CN102218907A - Image forming method - Google Patents

Image forming method Download PDF

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Publication number
CN102218907A
CN102218907A CN2011100789625A CN201110078962A CN102218907A CN 102218907 A CN102218907 A CN 102218907A CN 2011100789625 A CN2011100789625 A CN 2011100789625A CN 201110078962 A CN201110078962 A CN 201110078962A CN 102218907 A CN102218907 A CN 102218907A
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CN
China
Prior art keywords
water
image forming
forming method
ink
compound
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Granted
Application number
CN2011100789625A
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Chinese (zh)
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CN102218907B (en
Inventor
松本淳
安田浩司
入田洁
佐佐田美里
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers

Abstract

Provided is an image forming method including applying an ink that forms an image by inkjetting an ink composition containing coloring particles, a water-soluble polymerizable compound, a polymerization initiator and water onto a recording medium in which a base paper, a first layer containing a binder, and a second layer containing a white pigment are layered in this order, and a Cobb water absorption degree on a surface of the first layer placed on the base paper is 5.0 g/m2 or less as measured by a water absorption degree test according to JIS P8140 with a contact time of 15 seconds, and a water absorption amount on a surface of the second layer is 2 mL/m2 to 8 mL/m2 as measured by a Bristow method with a contact time of 0.5 seconds.

Description

Image forming method
Technical field
The present invention relates to a kind of image forming method.
Background technology
Ink-jet technology is used in fields such as office printer, household printer.In addition, in recent years, they just are being applied to commercial printing.In commercial printing, printing paper need have the printing sense similar to common printed paper, rather than is getting rid of the surface printing sense that printing ink solvent penetrates into the ink jet paper on the ink absorbing layer that forms on the resin-coated paper of body paper fully.
In addition, require the image of formation to have high-quality.
With above-mentioned be associated be, disclose when keeping printing sense by the Chinese white layer formation barrier layer of using binding agent and water absorption to be controlled, recording medium (for example, Japanese patent application is examined open (JP-A) No.2009-73158) with the curling of improvement and fold improvement.
In addition, disclose on the paper recording medium use photo curable aqueous monomers printing ink recording method (for example, JP-ANo.2001-323194).
Yet, even for the image forming method that uses the recording medium of putting down in writing among the JP-A No.2009-73158, also wish further to improve and curl and fold, also need further to improve cohesive to the image that forms.
In addition,, only put down in writing the image forming method that uses ink jet paper, can not obtain to have the printing material that common paper is felt like that according to JP-ANo.2001-323194.
Because the problems referred to above, the purpose of this invention is to provide and a kind ofly have the method for excellent fusible image by the medium that when forming image, suppresses to curl and the generation of fold forms the image that is used to write down formation.
Summary of the invention
Because above-mentioned situation has been finished the present invention, and a kind of image forming method is provided.
A first aspect of the present invention provides a kind of image forming method, and it comprises:
By on recording medium, spraying the ink composite that contains colored particles, water-soluble polymerizable compound, polymerization initiator and water, be coated with printing ink and form image, body paper in described recording medium (base paper), contain the ground floor of binding agent and contain the second layer stacked above one another of Chinese white, the absorption of water test according to JIS P8140 on the surface that is configured in the ground floor on the described body paper is 5.0g/m with the Cobb absorption of water of measuring 15 seconds time of contact 2Or littler, be 2mL/m according to the Bristow method with the water absorption of measuring time of contact of 0.5 second on the surface of the second layer 2～8mL/m 2
The disclosure of JIS P8140 is quoted and is incorporated among the application.
According to the present invention, can provide a kind of and have the method for excellent fusible image by the medium that when forming image, suppresses to curl and the generation of fold forms the image that is used to write down formation.
Description of drawings
The schematic diagram of Fig. 1 has shown the example of the structure of recording medium of the present invention.
The specific embodiment
＜image forming method 〉
Image forming method of the present invention comprises by ink ejecting method spray the ink composite that contains colored particles, water-soluble polymerizable compound, polymerization initiator and water on recording medium, be coated with printing ink and form image, in described recording medium body paper, contain the ground floor of binding agent and contain the second layer stacked above one another of Chinese white, the absorption of water test according to JIS P8140 on the surface that is configured in the ground floor on the described body paper is 5.0g/m with the Cobb absorption of water of measuring 15 seconds time of contact 2Or littler, be 2mL/m according to the Bristow method with the water absorption of measuring time of contact of 0.5 second on the surface of the second layer 2～8mL/m 2(below, can be called " specific recording medium ").
The ink composite that contains water-soluble polymerizable compound by coating on specific recording medium forms image, can form recording medium is had excellent adhesiveness and suppress the image of recording medium distortion as curling and fold when printing ink is coated with.
[printing ink application step]
According to printing ink application step of the present invention, the ink composite that utilizes ink-jet method to spray on specific recording medium to contain colored particles, water-soluble polymerizable compound, polymerization initiator and water forms image.In addition, provide detailed description below about recording medium and ink composite.
(ink-jet method)
Use the image record of ink-jet method ink composite to be ejected into to form rendered image above the recording medium and carry out by applying energy.In addition, as preferred ink jet recording method among the present invention, can use the method for putting down in writing in paragraph [0093]～[0105] of JP-ANo.2003-306623.
Ink-jet method is not particularly limited, and can be any known method, for example, and by utilizing the electric charge control method of electrostatic attraction ink jet; The dropping method as required (drop-on demand method) (pressure pulse method) of the oscillation pressure ink jet by utilizing piezoelectric element; By utilizing the sound ink-jet method of shining the radiation pressure ink jet of printing ink generation from the acoustic beam of signal of telecommunication conversion.
The ink gun that uses in the ink-jet method can be on-demand ink gun (on-demand type) or continuous ink jet head.The printing ink nozzle that uses when writing down by ink-jet method is not particularly limited, and can suitably select according to desired use.
In addition, the example of ink-jet method comprises that injection is known as the method for the low-density little droplet of ink of photograph printing ink in a large number; Use has substantially the same tone but the multiple inks of different densities is improved the method for picture quality; With the method for using clear, colorless printing ink.
In addition,, there is shuttle system (shuttle system), wherein when the width of recording medium moves, carries out record with scan mode at the short series head about ink-jet method; And linear system, wherein use linear head with tape deck of arranging corresponding to a side total length of recording medium.In linear system, by along perpendicular to the direction movable recording media of tape deck orientation, on one whole of recording medium, carry out the image record, thereby can omit the transportation system that moves brachycephaly portion with scan mode, as print cartridge.In addition, owing to do not need the complexity scanning-motion control that print cartridge and recording medium are moved and have only recording medium to move, so compare with shuttle system, writing speed can be improved.
From obtaining the viewpoint of HD image, the every quantity of ink that sprays from ink gun is 1pL～10pL (skin liter), more preferably 1.5pL～6pL.Inhomogeneous and improve the viewpoint of the flatness of continuous level (continuous gradation) from suppressing image, the drops of the different amounts of combined jet also are effective.The present invention also is effective in this embodiment.
The coating weight of ink composite on recording medium can be according to suitably selections such as required image densities.From the viewpoint of image cohesive and image density, the maximum coating weight of ink composite is preferably 3～30ml/m 2, more preferably 3～20ml/m 2, more preferably 5～15ml/m again 2
[treatment fluid application step]
Preferably, image forming method of the present invention also comprises the treatment fluid application step, the treatment fluid that will contain agglutinant by this treatment fluid application step is coated on the recording medium, and described agglutinant can form aggregation when described treatment fluid contacts with ink composite.By comprising the treatment fluid application step, can under higher speed, produce image with higher resolution.In addition, provide the detailed description of treatment fluid below.
According to the present invention, the order of carrying out treatment fluid application step and printing ink application step is not particularly limited.Yet,, preferably after the treatment fluid application step, carry out the printing ink application step from the viewpoint of picture quality.Specifically, preferably, the printing ink application step is that ink composite is applied to step on the recording medium that is coated with treatment fluid.
According to the treatment fluid application step, the treatment fluid that will contain the agglutinant of the component in can the aggegation ink composite is applied on the recording medium.Can use known method that treatment fluid is applied on the recording medium, not have specific limited, that is, can select any method, comprise spraying process, use the rubbing method of applicator roll, based on the rubbing method or the infusion process of ink-jet method.The detailed description of ink-jet method with provide above identical.
Can use known rubbing method to be coated with, be coated with machine, knife type coater, extrusion coating machine, reverse roll coater etc. as using doctor knife coater (bar coater), extrusion die coating machine, Kohler coater, scraper-type coating machine, rod.
In addition, can use the method that when utilization is equipped with the coating apparatus control coating weight of amount of liquid control piece, is coated with, as the coating apparatus of putting down in writing among the JP-ANo.10-230201.
Treatment fluid can be applied on the whole surface of recording medium.Selectively, treatment fluid can be applied on the zone of carrying out ink mist recording in the printing ink application step.According to the present invention, from even regulation treatment fluid coating weight, evenly write down fine rule, fine image section etc. and to suppress density unevenness even as the uneven viewpoint of image, preferably, by the method for using coating liquids such as applicator roll treatment fluid is applied on the whole surface of recording medium.
About the method for coating treatment fluid in the coating weight with treatment fluid controls to above-mentioned scope, can suitably mention the method for for example using anilox roll (anilox roller).Anilox roll is a kind of following roller, wherein has the roller surface of pottery to carry out Laser Processing to thermal spraying, and forms cone shaped pattern, oblique line pattern, hexagon pattern etc. from the teeth outwards.Treatment fluid enters and is formed in the lip-deep recess of roller, and when the roller surface contacts with paper, shifts, and the coating weight coating treatment fluid to be controlled by the recess of anilox roll.
[active energy beam irradiating step]
Preferably, image forming method of the present invention comprises the step that is coated on the ink composite on the recording medium with the active energy beam irradiation.When using the active energy beam irradiation, the polymerizable compound polymerization that comprises in the ink composite forms the cured film that contains colored particles.As a result, the cohesive of image, wearability and resistance to blocking more effectively improve.
The ink composite that is injected on the recording medium is solidified by the irradiation of active energy beam.This be because, the polymerization initiator that comprises in ink composite of the present invention shines and deterioration through active energy beam, releasers such as generation such as free radical, acid or alkali, releaser causes and promotes the polymerisation of polymerizable compound, thereby solidifies ink composite of the present invention.
Here, as active energy beam, can use α line, γ line, electron beam, X line, ultraviolet ray, luminous ray or infrared ray etc.The wavelength of active energy beam is preferably 200～600nm, more preferably 300～450nm, more preferably 350～420nm again.
In cumulative exposure, the output of active energy beam is preferably 5000mJ/cm 2Or littler, more preferably 10～5000mJ/cm 2, more preferably 10～2000mJ/cm again 2, further more preferably 20～2000mJ/cm again 2When the cumulative exposure of active energy beam fell in the above-mentioned scope, the cohesive of image was more effectively improved.
As the active energy beam source, mainly utilize mercury vapor lamp and gas or solid state laser etc., as the light source that ultraviolet photo-curing type ink-jet recording ink is used, mercury vapor lamp and metal halide lamp are extensively known.Yet recently year, from the viewpoint of environmental protection, mercury is used in strong not hope, uses GaN semiconductor UV-light luminous device very useful from the viewpoint of industry and environment.In addition, LED (UV-LED) and LD (UV-LD) have advantage small-sized, that the life-span is long, efficient is high and cost is low, and people expect to use them as light-cured type ink-jet light source.
In addition, can use light emitting diode (LED) and laser diode (LD) as the dynamic rays source.Especially, needing to use UV-LED or UV-LD under the situation of ultraviolet source.For example, the ultraviolet LED of the light of wavelength in the 365nm～420nm scope of mainly sending of Nichia Corporation sale.
In the present invention, UV-LED is particularly preferred active energy beam source, and peak wavelength is that the UV-LED of 350～420nm is particularly preferred.
[ink setting step]
Image forming method of the present invention can comprise drying and the printing ink solvent of removing in the ink composite that is applied on the recording medium (example comprises water and water-miscible organic solvent) when needed.The ink setting step is not particularly limited, as long as can remove a part of printing ink solvent at least in this step, can use any common method.
For example, can use known heating unit such as heater, the blasting unit that utilizes air blast such as drying machine or its combination to carry out ink setting.The example of heating means comprises: use heater etc. apply the method for heat from the treatment fluid coated face opposition side of recording medium; To the treatment fluid coated face blowing warm air of recording medium or the method for hot blast; With the heating means of using infrared heater etc.Can be used in combination these methods heats.
In addition, the ink setting step is carried out after the printing ink application step, and can carry out before or after the active energy beam irradiating step.According to the present invention,, preferably before the active energy beam irradiating step, carry out the ink setting step from solidifying the viewpoint of sensitivity and resistance to blocking.
Below, illustrate in greater detail the recording medium, ink composite and the treatment fluid that use in the image forming method of the present invention.
[recording medium]
Recording medium of the present invention comprises stacked in turn body paper, ground floor and the second layer, also comprises other layers of suitably selecting according to purposes when needed.
For example, as shown in Figure 1, recording medium 100 comprises high quality paper 11, solvent barrier layer 12 that is used as ground floor that is used as body paper and the ink absorbing layer 13 that is used as the second layer, and wherein solvent barrier layer 12 is formed on the high quality paper 11, and ink absorbing layer 13 is formed on the solvent barrier layer 12.
In addition, recording medium can be any in sheet-fed and the roll web.
(body paper)
Body paper is not particularly limited, and can suitably select from as known in the art those according to desired use.
About being used as the paper pulp of the raw material of body paper, from increasing surface smoothness, rigidity and dimensional stability (crimpiness) viewpoint simultaneously, preferred broad-leaved bleached kraft pulp (LBKP) to gratifying level.Yet needle bleached kraft pulp (NBKP) and broad-leaved bleaching sulfite pulp (LBSP) etc. also can use.
Paper pulp can use beater or material homogenizer making beating.If needed, the slurry that after pulling an oar, forms (below, can be called " paper pulp raw material ") the various additives of middle adding.The example of additive comprises filler, dried paper reinforcing agent, sizing agent (sizing agent), l Water Paper reinforcing agent, color-fixing agent, pH conditioning agent and other reagent.
The example of filler comprises calcium carbonate, clay, kaolin, carclazyte (white clay), talcum, titanium dioxide, diatomite, barium sulfate, aluminium hydroxide and magnesium hydroxide.The example of dried paper reinforcing agent comprises cationic starch, PAMC, PAMA, amphiprotic polyacrylamide and carboxy-modified polyvinyl alcohol.The example of sizing agent comprises soap, rosin, rosin derivative (for example, maleic rosin), paraffin, alkyl ketene dimer, alkenyl succinic anhydride (ASA) and epoxidised fatty acid amide.
The example of l Water Paper reinforcing agent comprises polyamine polyamide epichlorohydrin, melmac, urea resin and epoxidised polyamide.The example of color-fixing agent comprises such as multivalent metal salts such as aluminum sulfate and aluminium chloride with such as cationic polymers such as cationic starches.The example of pH conditioning agent comprises caustic soda and sodium carbonate.
The example of other reagent comprises defoamer, dyestuff, foundry loam controlling agent and fluorescent whitening agent.If needed, can also add softening agent.The example of softening agent comprises those that for example put down in writing in " New edition-Paper and Paper Treatment Manual (SHIGYO TIMES publishes, 1980) (pp.554～555) ".
The treatment fluid that is used for surperficial starching processing can contain water-soluble polymer, sizing agent, resistance to water compound, pigment, pH conditioning agent, dyestuff and fluorescent whitening agent etc.The example of water-soluble polymer comprises the sodium salt and the kayexalate of cationic starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethylcellulose, sulfate cellulose, gelatin, casein, Sodium Polyacrylate, styrene-maleic anhydride copolymer.
The example of sizing agent comprises ammonium salt, rosin, higher fatty acid salt, alkyl ketene dimer (AKD) and the epoxidised fatty acid amide of petroleum resin emulsion, styrene-maleic anhydride copolymer Arrcostab.
The resistance to water examples for compounds comprises latex or the emulsion and the polyamide polyamine chloropropylene oxide of SB, vinyl-vinyl acetate copolymer, polyethylene, vinylidene chloride copolymer etc.
The example of pigment comprises calcium carbonate, clay, kaolin, talcum, barium sulfate and titanium dioxide.The example of pH conditioning agent comprises hydrochloric acid, caustic soda and sodium carbonate.
Mixed paper and various combination paper that the example of body paper comprises the natural slurry paper that formed by above-mentioned paper pulp, synthetic pulp paper, formed by natural pulp and synthetic paper-pulp.The thickness of body paper for example is 30 μ m～500 μ m, preferred 50 μ m～300 μ m, more preferably 70 μ m～200 μ m.
(ground floor)
Ground floor is not particularly limited, and is 5.0g/m as long as it contains binding agent and tests the Cobb absorption of water of measuring with 15 seconds time of contact by the absorption of water of JIS P8140 regulation 2Or littler, and can suitably select from as known in the art those according to purpose.Here, be placed on ground floor and the surface opposing that side of body paper on the body paper at the absorption of water test of the JIS P8140 of the body paper that is formed with ground floor on it regulation and carry out.
For example, the body paper that is formed with ground floor on it is 2.0g/m by the absorption of water test of JIS P8140 regulation with the Cobb absorption of water of measuring 2 minutes time of contact 2Or littler, the body paper that is formed with ground floor on it uses diethylene glycol to replace water to be 5.0g/m with the Cobb value of measuring 2 minutes time of contact by the absorption of water test of JIS P8140 regulation 2Or it is littler; ground floor contains at least a thermoplastic resin and polyvinyl alcohol (especially; the degree of polymerization is 1; 000 or bigger acetoacetyl modified polyethylene alcohol be preferred) as binding agent; ground floor also contains layered inorganic compound; ground floor contains polyvinyl alcohol and layered inorganic compound simultaneously; wherein quality of polyvinyl alcohol (X) and ratio as the quality (Y) of the hydroexpansivity synthetic mica of layered inorganic compound; promptly; X/Y is 1～30; ground floor also contains curing agent, and preferred ground floor also contains Chinese white.
The absorption of water test that the body paper that is formed with solvent barrier layer (ground floor) on it is pressed JIS P8140 regulation with the Cobb absorption of water measured 15 seconds time of contact greater than 5.0g/m 2The time, may exist paper intensity to reduce and because the situation of the distortion that causes of preventing to expand unsatisfactorily.
On the other hand, be 2.0g/m when testing the Cobb absorption of water of measuring with 2 minutes time of contact by the absorption of water of JIS P8140 regulation 2Or it is littler and use diethylene glycol to be 5.0g/m with the Cobb value of measuring time of contact of 2 minutes according to JIS P8140 program 2Or more hour, can prevent fully almost that paper intensity from reducing and because the distortion that causes of expanding (for example, curl and fold).
Concrete solution at the problems referred to above is, will be insoluble by disperse water in the aqueous dispersion of particulate form or the coating fluid that mainly contains water dispersible latex of slightly water-soluble hydrophobic polymer preparation on each surface with 3g/m 2～20g/m 2Amount of solid be coated on the body paper, the result obtains resistance to water almost completely.
In addition,, that is, do not repel water, add Chinese white, form the solvent barrier layer by the amount of aftermentioned binding agent 5 mass parts～50 mass parts of per 100 mass parts in order to make the resin surface possess hydrophilic property.The base paper sheet that is formed with ground floor on its that obtains reveals abundant resistance to water and can be coated with the second layer easily.
In addition, by use the ratio of width to height be 30 or bigger Chinese white as Chinese white, its amount can increase to binding agent 200 mass parts by per 100 mass parts.In addition, use this Chinese white not only to allow to be coated with the second layer easily, and have the excellent property handled, excellent clean-up performance.
-binding agent-
Binding agent contained in the ground floor is not particularly limited, as long as this layer contains at least a thermoplastic resin and polyvinyl alcohol.Preferably, it contains thermoplastic resin.
-thermoplastic resin-
Thermoplastic resin is not particularly limited, and can (for example, the homopolymers of alpha-olefin is as polyethylene and polypropylene from known thermoplastic resin such as vistanex; Mixture with homopolymers) and the latex of thermoplastic resin suitably select.Wherein, latex preferably, as polyester-polyurethane latex, acrylic latex, acrylic acid silicone latex, acrylic acid epoxy latex, acrylic acid styrene latex, acroleic acid polyurethane latex, styrene-butadiene latex, acrylonitrile-butadiene latex and vinyl acetate latex, and be preferably selected from wherein at least a.Wherein, especially, the preferred use is selected from least a of polyester-polyurethane latex and acrylic acid silicone latex.
The example of polyester-polyurethane latex comprises Dainippon Ink and Chemicals, HYDRAN AP series and HYDRAN ECOS series (trade name) that Inc. produces.
Aforementioned acrylic latex can be the commercially available prod.For example, can use following water dispersible latex.The example of acrylic resin comprises Daicel Chemical Industries, " NIPOL Lx 811,814,821,820 and 857 " (trade name) that " CEVIAN A4635,46583 and 4601 " (trade name) that Ltd. produces and Zeon Corporation produce.
Especially, the acrylic emulsion that can suitably use the acrylic acid silicone latex of putting down in writing among JP-ANo.10-264511,2000-43409,2000-343811 and the 2002-120452 (specifically, for example, commercially available Daicel Chemical Industries, " AQUABRID SERIESUM7760, UM7611, UM4901, MSi-045, ASi-753, ASi-903, ASi-89, ASi-91, ASi-86,4635, MSi-04S, AU-124, AU-131, AEA-61, AEC-69 and AEC-162 " (trade name) that Ltd. produces).
Above-mentioned thermoplastic resin can use separately or two or more can be used in combination.
Preferred its glass transition temperature (Tg) of thermoplastic resin is 5 ℃～70 ℃, preferred especially 15 ℃～50 ℃.By having the Tg of this scope, can avoid forming the property handled difficulty in the preparation process that problem that the aggregation of the liquid (for example, coating fluid) of ground floor produces causes.In addition, can not cause following problem, comprise because Tg is too high and can not therefore can easily obtain high gloss and high flatness in the problem that does not have the required gloss of acquisition under the significantly high calender temperature with owing on the metallic roll surface, have the problem that high adherence makes the surface state deterioration.
Preferred its MFT of thermoplastic resin is 20 ℃～60 ℃, more preferably 25 ℃～50 ℃.By regulating minimum required film-forming temperature in above-mentioned scope, the liquid of formation ground floor (for example, coating fluid) can in preparation process, not relate in the processing hell and high water (for example, produce burr), in the process that forms the second layer, the surface appearance of the second layer that forms is not because higher infiltration and deterioration can form required microporous layers allows the printing ink solvent rapid permeability.The layer that obtains behind the coating liquid (for example, coating fluid) can not show excellent glossiness, yet, handle by carrying out the back calendering, can obtain to have micro porous high glaze layer.
Press the solid content meter of ground floor, the thermoplastic resin content in the ground floor is preferably 15～95 quality %, more preferably 30～90 quality %.When content is adjusted to when falling in the above-mentioned scope, under the situation of not damaging glossiness after rolling processing and flatness, has obtained sufficient printing ink solvent permeability, thereby prevented that effectively the printing ink that takes place as time passes from oozing out.
-polyvinyl alcohol-
Except common polythene alcohol (PVA), polyvinyl alcohol comprises cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol modified polyethylene alcohol, pure and mild other polyvinyl alcohol derivatives of acetoacetyl modified polyethylene.Polyvinyl alcohol can use separately or two or more can be used in combination.Wherein, can preferably use polyvinyl alcohol and acetoacetyl modified polyethylene alcohol.
According to the present invention, the saponification degree of polyvinyl alcohol is preferably 70%～99%, and more preferably 85%～99%.In addition, the degree of polymerization is preferably 1000～4500, and more preferably 1500～4500.By regulating the saponification degree and the degree of polymerization, can obtain sufficient film-strength and extensibility to above-mentioned scope.
-Cobb absorption of water-
Absorption of water thermometrically Cobb absorption of water according to JIS P8140 regulation.In this test, make a surface of paper contact the scheduled time, and measure the water yield that paper absorbs with water.In addition, be set at 15 seconds time of contact or 2 minutes.
In addition, according to the present invention, be placed on and carry out the absorption of water measurement on ground floor and the surface opposing that side of body paper on the body paper.
-Cobb value-
Based on the absorption of water test program of JIS P8140 regulation, using diethylene glycol to replace water and time of contact is to measure the Cobb value in 2 minutes.In this is measured, make a surface of paper contact the scheduled time, and measure the diethylene glycol amount that paper absorbs with diethylene glycol.
In addition, according to the present invention, be placed on and carry out the measurement of diethylene glycol liquid absorption on ground floor and the surface opposing that side of body paper on the body paper.
-layered inorganic compound-
Preferably, ground floor also contains layered inorganic compound.The preferred embodiment of layered inorganic compound comprises dilatancy layered inorganic compound such as the synthetic terre verte of expansive clay mineral (as bentonite, hectorite, saponite, bidelite, nontronite, stivensite, beidellite and imvite), dilatancy synthetic mica and dilatancy.These dilatancy layered inorganic compounds have the layer structure that the monocrystalline compartment by thickness 1nm～1.5nm forms, and compare with other clay minerals, and the metallic atom substitution value in the lattice significantly improves.As a result, the positive charge shortage appears in the lattice layer, and in order to remedy shortage, Na +, Ca 2+, Mg 2+And other cations are adsorbed between the layer.These place the cation between the layer to be called exchange cation, can with various cation exchange.Especially, the cation between layer is Li +, Na +During with other ions, because ionic radius is little, the combination between the layer winding is very weak, and water significantly expands.In this state, when applying shearing force, rupture easily, form the stable hydrosol.Bentonite and dilatancy synthetic mica show strong this behavior, and preferred for the objective of the invention is.Especially, the hydroexpansivity synthetic mica is preferred.
The example of hydroexpansivity synthetic mica comprises Na-four silicon mica (NaMg 2.5(Si 4O 10) F 2Na), Li-taincolite ((NaLi) Mg 2(Si 4O 10) F 2Na) and Li-montmorillonite ((NaLi)/3Mg 2/ 3Li 1/3(Si 4O 10) F 2).
The thickness of the hydroexpansivity synthetic mica that preferably uses among the present invention is 1nm～50nm, and face is of a size of 1 μ m～20 μ m.From the viewpoint of preferred its diffusion of control, thickness is preferably less than the maximum possible degree; The face size is preferably greater than the maximum possible degree, as long as it falls into the surface smoothing of coating and the scope that the transparency does not have deterioration of making.Therefore, the ratio of width to height is preferably 100 or bigger, and more preferably 200 or bigger, preferred especially 500 or bigger.
-mass ratio-
In ground floor, the ratio of the quality (X) of acetoacetyl modified polyethylene alcohol and the quality (Y) of hydroexpansivity synthetic mica, that is, X/Y is preferably 1～30, and more preferably 5～15.When mass ratio falls in 1～30 the scope, can prevent block infiltration and bubble formation effectively.
-curing agent-
Curing agent contained in the ground floor of the present invention is characterised in that it is at least a compound that is selected from following material: the aldehyde based compound; 2,3-dihydroxy-1,4-diox and its derivative; With the compound that in a molecule, has 2 or more vinyl, the contiguous Hammett substituent constant of described vinyl σ pBe positive substituting group.By containing at least a following compound: the aldehyde based compound; 2,3-dihydroxy-1,4-diox and its derivative; With the compound that in a molecule, has 2 or more vinyl as the curing agent in the ground floor of the present invention, the contiguous Hammett substituent constant of described vinyl σ pBe positive substituting group, itself and acetoacetyl modified polyethylene alcohol react, thereby strengthen the resistance to water of the recording medium that forms, and not thickening ground floor coating fluid.As a result, the improvement of acquisition resistance to water and the wherein recording medium of the more stable coating of ground floor coating fluid.
Hammett substituent constant σ pFor positive substituent example comprises CF 3Group (σ p0.54), CN group (σ value: p0.66), COCH value: 3Group (σ p0.50), COOH group (σ value: p0.45), COOR (R represents alkyl) group (σ value: p0.45), NO value: 2Group (σ p0.78), OCOCH value: 3Group (σ p0.31), SH group (σ value: p0.15), SOCH value: 3Group (σ p0.49), SO value: 2CH 3Group (σ p0.72), SO value: 2NH 2Group (σ p0.57), SCOCH value: 3Group (σ p0.44), F group (σ value: p0.06), Cl group (σ value: p0.23), Br group (σ value: p0.23), I group (σ value: p0.18), IO value: 2Group (σ p0.76), N value: +(CH 3) 2Group (σ pValue: 0.82), and S +(CH 3) 2Group (σ pValue: 0.90).
In a molecule, have 2 or more contiguous Hammett substituent constant σ pFor the examples for compounds of positive substituent vinyl comprises 2-ethene sulfonyl-N-[2-(2-ethene sulfonyl-acetyl-amino)-ethyl] acetamide, two-2-vinylsulfonyl ethylether, two acrylimide, N; N '-two propylene uride, 1,1-bi-vinyl sulfone ethane, ethene-two-acrylamide and and the diacrylate ester compounds and the dimethylacrylate compound of following structural formula representative.Wherein, 2-ethene sulfonyl-N-[2-(2-ethene sulfonyl-acetyl-amino)-ethyl] acetamide is particularly preferred.
CH 2＝CHCOO(CH 2CH 2O) n-COCH＝CH 2
n＝4，n＝9
Figure BSA00000463194400131
n＝4.n＝9
In ground floor,, in a molecule, have 2 or more contiguous Hammett substituent constant σ with respect to polyvinyl alcohol pFor the amount of the compound of positive substituent vinyl is preferably 0.1～30 quality %, more preferably 0.5～10 quality %.When its amount is 0.5～10 quality % with respect to polyvinyl alcohol, can improve the resistance to water of the recording medium of formation effectively, and not thickening ground floor coating fluid.As a result, show the Expected Results that uses the above-claimed cpd among the present invention.
-Chinese white-
The example of Chinese white comprises titanium dioxide, barium sulfate, brium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica, antimony trioxide, titanium phosphate, aluminium hydroxide, kaolin, clay, talcum, magnesia and magnesium hydroxide.These can use separately or two or more can be used in combination.Wherein, kaolin is particularly preferred.
-kaolin-
Preferred its ratio of width to height (diameter/thickness) of kaolin is 30 or bigger.The ratio of width to height be 30 or bigger kaolinic example 59) and Astra-Plate (the ratio of width to height: 34)) comprise engineering level kaolin (for example, Contour 1500 (the ratio of width to height:.When kaolin had high whiteness and precipitous size distribution (uniform grading), recording medium had excellent whiteness and printability.
About the particle diameter of Chinese white, preferred 75% or the particle diameter of more Chinese white be 2 μ m or littler, average grain diameter is preferably 0.1 μ m～0.5 μ m.Specifically, by having the particle diameter in this scope, can avoid whiteness to descend effectively or glossiness decline.
Titanium dioxide can be any in anatase titanium dioxide or the rutile-type.They can be used singly or in combination.In addition, titanium dioxide can pass through sulphation method or chloride process production.Titanium dioxide can suitably be selected from those that carry out with inorganic compound (as hydrated alumina, hydrated SiO 2 or zinc oxide) that face coat handles; Those that carry out that face coat handles with organic compound (as Pehanorm, trimethylolethane, trimethylolpropane or 2,4-dihydroxy-2-methylpentane); With handle with siloxanes such as dimethyl silicone polymer those.
The refractive index of Chinese white is preferably 1.5 or bigger.By containing the Chinese white of refractive index in above-mentioned scope, can obtain to have high-quality image.
In addition, the specific area preferably measured according to the BET method of Chinese white is less than 100m 2/ g.By containing the Chinese white of specific area in this scope, can suppress the coating fluid infiltration and the formation coating and the formation second layer, thereby strengthen the ink absorption of the second layer.
Here, the BET method is a kind of long-pending measuring method of powder surface of utilizing gas phase adsorption method.In the method, determine the total surface area (that is specific area) of 1g sample from adsorption isothermal curve.Usually, nitrogen is as adsorbed gas.Generally measure the gas flow of sample absorption based on the pressure or the Volume Changes of gas.The most famous equation of representing the polymolecular adsorption isothermal curve is Brunauer Emmett, Teller equation (that is BET equation).Calculate adsorbance from this equation, and with the area that occupies with an absorbing molecules on duty that obtains, thereby definite surface area.
Chinese white content in the ground floor is with the type and the layer thickness variation of Chinese white and thermoplastic resin.In general, by the thermoplastic resin of per 100 mass parts, preferred about 50 mass parts are to about 200 mass parts.
In addition, ground floor can contain known additives, as antioxidant.
The thickness of the ground floor that forms from composition is preferably 1 μ m～30 μ m, more preferably 5 μ m～20 μ m.When layer thickness is adjusted to when falling in the above-mentioned scope, show high gloss through the laminar surface of calendering.In addition, also can make the surface have whiteness by using a spot of Chinese white, and can be suitable with coated paper or art printing paper aspect property handled such as folding property.By Chinese white being added to the another kind of advantageous effects that obtains in the ground floor is the cohesive that prevents in the calender line of coating behind the ground floor calender.
(second layer)
The second layer is not particularly limited, as long as it contains Chinese white and is 2mL/m according to the Bristow method with the water absorption of measuring time of contact of 0.5 second 2～8mL/m 2, can according to purpose be selected from as known in the art those.Preferably, for example, the second layer uses the liquid of the diethylene glycol that contains 30 quality % in pure water to be 1mL/m with the liquid absorption of measuring 0.9 second time of contact according to the Bristow method 2～6mL/m 2, the second layer also contains binding agent, and with respect to the Chinese white of 100 mass parts, the second layer contains the thermoplastic resin of 10 mass parts～60 mass parts by solid content meter, and preferred film surface p H is the acid second layer.
In addition, according to the present invention, the second layer with the opposing face side of ground floor on carry out the second layer according to the Bristow method lip-deep liquid absorption measure.
The second layer according to the Bristow method with the water absorption measured time of contact of 0.5 second greater than 8mL/m 2The time, recording medium shows high printing ink solvent infiltration rate, thereby causes poor agglutinating reaction near surface.As a result, when for example using fixing roller, printing ink is transferred on the fixing roller, thereby causes printing material to defile.
In addition, when water absorption less than 2mL/m 2The time, solvent is encapsulated in the aggegation process of printing ink, thereby causes the anamorphose problem.
In addition, when the liquid that uses the diethylene glycol in pure water, contain 30 quality % according to the Bristow method (almost near the actual printing ink that uses) with the liquid absorption measured 0.9 second time of contact greater than 6mL/m 2The time, above-mentioned same problem takes place; That is, cause on the print product and defile.When liquid absorption less than 1mL/m 2The time, cause the anamorphose problem.
Making the second layer is 2mL/m according to the Bristow method with the water absorption of measuring 0.5 second time of contact 2～8mL/m 2(preferably, use the liquid of the diethylene glycol that in pure water, contains 30 quality % to be 1mL/m with the liquid absorption of measuring 0.9 second time of contact according to the Bristow method 2～6mL/m 2) concrete solution be, the binder content of the second layer to be adjusted to 5 mass parts～15 mass parts by the Chinese white of 100 mass parts.
-Chinese white-
Chinese white is not particularly limited, and can be selected from those of in copperplate paper Chang Zuowei Chinese white: for example, and calcium carbonate, kaolin, titanium dioxide, aluminium hydroxide, zinc oxide, barium sulfate, satin white and talcum.By Chinese white being added to the advantageous effects that obtains in the second layer is that the granules of pigments that comprises in the ink composite can be in being retained in the second layer.
Preferably, Chinese white only is made of less than the Chinese white of 8.0 (preferred below 7.5) the pH that measures according to the pH value method of testing of stipulating among the JIS K5101 (room temperature extraction method).If pH is greater than 8.0, then the surface p H of the second layer increases, and may occur that image oozes out and because the image quality decrease that the drop deformation behind the drippage causes.Can think that for example, because the general colored particles in the ink composite has anionic charge (that is, anionic property dissociate group), so the colored particles dispersion is relatively stable, make the aggegation of colored particles be not easy to take place.
In addition, according to the pH value method of testing of stipulating among the JIS K5101,0.1mL hydrochloric acid (1mol/L) is being added to pH that 10g measures the Chinese white of measuring behind the liquid less than 6.0 (preferred 5.0 or littler, more preferably 4.0 or littler).If pH is less than 6.0, the surface p H of the second layer raises and is suppressed, and makes image blurring and picture quality is improved.In addition, if use acidic materials etc. are adjusted to very low gathering with the promotion colored particles with the pH of the second layer, then Chinese white is neutralized, and surface p H rising is suppressed, make the pH regulating effect improve, can suppress image blurring effectively and the picture quality reduction.
The example of pigment comprises the mixture of kaolin, titanium dioxide and kaolin and titanium dioxide.
The content of Chinese white in the second layer is preferably 50～98 quality %, more preferably 70～97 quality %.
-Bristow method-
The Bristow method is to measure the most universal method of liquid uptake at short notice, and by Japan Technical Association of the Pulp and Paper Industry (J ' TAPPI) adopt.Write up is in J ' TAPPI No.51 " Kami, Itagamino Ekitai Kyushusei Shiken Houhou (Test Method for Liquid Absorbability of Paper and Paper Board) ".When measuring, according to the seam of the head box in the surface tension adjustment Bristow method of printing ink (head box slit) width.In addition, test fluid is not considered from the point of paper back side leakage.
-binding agent (thermoplastic resin)-
The second layer preferably contains at least a binding agent (thermoplastic resin).Binding agent (thermoplastic resin) is not particularly limited, for example can be identical with used those in the ground floor.With respect to the Chinese white of 100 mass parts, the content of binding agent in the second layer is preferably 2 mass parts～50 mass parts, more preferably 3 mass parts～30 mass parts.
-laminar surface pH-
Be adjusted to acidity by laminar surface pH, printing ink aggegation and can improve the printing ink photographic fixing with the second layer.
The laminar surface pH of the second layer before pH regulates is preferably less than 8.0, and more preferably 7.5 or littler.Before regulating, make laminar surface pH, can suppress image blurring and the picture quality reduction less than 8.0 at pH.In addition, when very low when promoting the gathering of colouring agent by using acid etc. that the pH of the second layer is adjusted to, Chinese white is neutralized, and surface p H raises and be suppressed, and makes the pH regulating effect improve, and can suppress image blurring and picture quality reduces.
In addition, the laminar surface pH of the second layer after pH regulates is preferably 5.5 or littler, and more preferably 4.5 or littler.If the laminar surface pH after pH regulates is 5.5 or littler, can suppress image blurring and the picture quality reduction.
Can measure surperficial pH by the method A (rubbing method) of regulation among the Japan Technical Association of the Pulp and Paper Industry (J.TAPPI).Specifically, for example, can use " pH Indicator Set for Surface of Paper " (Corp. produces for model MPC, KYORITSU CHEMICAL-CHECK Lab.) that is equivalent to method A to measure.
Can be by regulating in the coating fluid that acidic materials is added to the second layer or by carrying out pH on the surface that acidic materials is added to recording medium.Yet, preferably regulate by carrying out pH on the surface that acidic materials is added to recording medium.Specifically, preferably be added to and carry out pH on the surface of recording medium and regulate by the treatment fluid that will contain acidic materials.
The example of acidic materials comprises compound and its salt that contains phosphate radical, phosphonate radical, phosphinic acids root, sulfate radical, sulfonate radical, sulfinic acid root or carboxylate radical, more preferably contains the compound of phosphate radical, sulfonate radical or carboxylic acid.
The examples for compounds that contains phosphate radical comprises phosphoric acid, polyphosphoric acids, metaphosphoric acid, its derivative and its salt.The examples for compounds that contains sulfonate radical comprises methanesulfonic acid, poly sulfonic acid, its derivative and its salt.The examples for compounds that contains carboxylate radical comprises oxalic acid, tartaric acid, malic acid, malonic acid, citric acid, fumaric acid, maleic acid, butanedioic acid, salicylic acid, phthalic acid, lactic acid, acetate, trichloroacetic acid, monoxone, polyacrylic acid, its derivative and its salt.In addition, the example comprises having carboxyl as functional group and compound with furans, pyrroles, pyrrolin, pyrrolidones, pyrones, thiophene, indoles, pyridine or quinoline structure, as 2-pyrrolidone-5-carboxylic acid, pyrone carboxylic acid, pyrroles's carboxylic acid, furancarboxylic acid, picolinic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, its derivative and its salt.In addition, also can use inorganic acid example hydrochloric acid, sulfuric acid and nitric acid.
(other layers)
Other layers of recording medium are not particularly limited, and can suitably select according to desired use.
[method for preparing recording medium]
Recording medium of the present invention can be according to method preparation commonly used.For example, recording medium of the present invention can prepare according to the preparation method of record in paragraph [0076]～[0087] of JP-A No.2009-73158.
[ink composite]
Ink composite of the present invention contains at least a colored particles, at least a water-soluble polymerizable compound, at least a polymerizable compound and water and other components when needed.
(colored particles)
Can use known dyestuff, pigment etc. as colored particles, without limits.Wherein, from the viewpoint of printing ink coloring, colouring agent water insoluble basically or that be insoluble in water is preferred.Its instantiation comprises various pigment, disperse dyes, oil-soluble dyes and can form the illuminating colour of J aggregation.In addition, from sunproof viewpoint, pigment is preferred.
Pigment type according to the present invention is not particularly limited, and can use conventional known organic pigment or inorganic pigment.
The instantiation of organic pigment comprises AZOpigments, encircles pigment more, dyestuff chelate, nitropigments, nitroso pigments and nigrosine.Wherein, AZOpigments and many ring pigment are preferred.The example of AZOpigments comprises azo lake, insoluble azo colour, condensed azo pigment and chelate AZOpigments.The example of many ring pigment comprises phthalocyanine color, perylene pigment, purple cyclic ketones pigment, anthraquinone pigment, quinacridone pigment, dioxazine violet cyclic ketones pigment, indigo-blue pigment, thioindigo color, isoindoline pigment and quinophthalone pigment.The example of dyestuff chelate comprises basic dye type chelate and acid pigment type chelate.
In addition, the example of inorganic pigment comprises titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminium hydroxide, baryta yellow, cadmium red, chrome yellow and carbon black.Wherein, carbon black is particularly preferred.In addition, the example of carbon black comprises those that produced by known method (for example, contact method, oven process or hot method etc.).
The instantiation of operable pigment comprises the pigment of putting down in writing in paragraph [0142]～[0145] of JP-A No.2007-100071 among the present invention.
In addition, under using the situation of dyestuff, can use the dyestuff that keeps on the water insoluble carrier as the colouring agent among the present invention.About dyestuff, can use known dyestuff and do not have specific limited.For example, can suitably use dyestuff of putting down in writing among JP-A No.2001-115066, JP-A No.2001-335714 and the JP-A No.2002-249677 etc. among the present invention.In addition, carrier is not particularly limited, and needs only it and is insoluble in water or is indissoluble in water, and can use inorganic material, organic material or its composite.Specifically, can suitably use the carrier of putting down in writing among for example JP-ANo.2001-181549 and JP-ANo.2007-169418 among the present invention.
Keep the carrier (colouring agent) of dyestuff to can be used as it is or can be used in combination with dispersant when needed.As dispersant, can suitably use following dispersant.
Two or more pigment combinations that pigment can use separately or be selected from above-mentioned group are used, or use with the pigment combinations that is selected from not on the same group.
From the viewpoint of color density, granularity, ink stability and injection reliability, with respect to the gross weight of ink composite, () content is preferably 1～25 quality % to colored particles especially, pigment, more preferably 5～20 quality %.
-dispersant-
Contain in colored particles of the present invention under the situation of pigment, colouring agent is preferably formed the colored particles of utilizing dispersant to disperse in aqueous solvent.About dispersant, can use polymeric dispersant or low-molecular-weight surfactant type dispersant.In addition, polymeric dispersant can be any in water-soluble polymer dispersant and the insoluble polymer dispersant.
The dispersion stabilization in the time of from be used in ink-jet method and the viewpoint of ejection, among the present invention, the insoluble polymer dispersant is preferred.
-insoluble polymer dispersant-
Be not particularly limited according to insoluble polymer dispersant of the present invention (below, can be called for short work " dispersant "),, can use conventional known insoluble polymer dispersant as long as it is an insoluble polymer and can dispersed color.The insoluble polymer dispersant can comprise for example hydrophobic structure unit and hydrophilic structure unit simultaneously.
The monomer that constitutes the hydrophobic structure unit can be styrenic monomers, (methyl) alkyl acrylate and (methyl) acrylate that contains aromatic group etc.
The monomer that constitutes the hydrophilic structure unit is not particularly limited, as long as it is the monomer that contains hydrophilic radical.Hydrophilic radical can be non-ionic group, carboxyl, sulfonate radical or phosphonate radical etc.In addition, the nonionic examples of groups comprises hydroxyl, amide group (wherein nitrogen-atoms is not substituted), stems from the epoxy alkyl polymer group of (for example, poly-epoxy and PPOX etc.) and stems from the group of glycitols.
From the viewpoint of dispersion stabilization, preferably contain carboxyl at least according to hydrophilic structure of the present invention unit, and the structure that contains nonionic group and carboxyl simultaneously is preferred.
The instantiation of the insoluble polymer dispersant among the present invention comprises styrene-(methyl) acrylic copolymer, styrene-(methyl) acrylic acid-(methyl) acrylate copolymer, (methyl) acrylate-(methyl) acrylic copolymer, polyethylene glycol (methyl) acrylate-(methyl) acrylic copolymer and styrene-maleic acid copolymer.
Here, " (methyl) acrylic acid " refers to acrylic or methacrylic acid.
In the present invention, viewpoint from dispersing of pigments stability, the insoluble polymer dispersant preferably contains the polyvinyl of carboxyl, more preferably contains the construction unit that stems from the monomer that contains aromatic group at least as the hydrophobic structure unit with contain the polyvinyl of the construction unit of carboxyl as the hydrophilic structure unit.
From the viewpoint of dispersing of pigments stability, the weight average molecular weight of insoluble polymer dispersant is preferably 3,000～200, and 000, more preferably 5,000～100,000, more more preferably 5,000～80,000, preferred especially 10,000～60,000.
From the viewpoint of dispersing of pigments, printing ink coloring and dispersion stabilization, with respect to pigment, the content of dispersant in colored particles is preferably 10～100 quality % in the present invention, more preferably 20～70 quality %, preferred especially 30～50 quality %.
When dispersant in colored particles content in above-mentioned scope the time, pigment tends to be covered by the dispersant of suitable amount, and can easily obtain to have the colored particles of small particle diameter and excellent ageing stability.
Except the insoluble polymer dispersant, the colored particles among the present invention can also contain other dispersants.The example of operable other dispersants comprises known water-soluble low molecular weight dispersant and water-soluble polymer.The content of the dispersant outside the insoluble polymer dispersant for example can be in the above-mentioned scope of dispersant.
From the viewpoint of dispersion stabilization and ejection, colored particles of the present invention preferably is made of pigment and insoluble polymer dispersant, and preferably, at least a portion surface of pigment is covered by the insoluble polymer dispersant.Can obtain colored particles by the mixture that uses dispersing apparatus to disperse to contain pigment, dispersant and when needed (preferably, organic solvents) such as solvents as the colored particles dispersion.
Prepare as follows according to colored particles dispersion of the present invention: the aqueous solution that will contain alkaline matter is added in the mixture of the organic solvent that contains pigment, insoluble polymer dispersant and can dissolve or disperse dispersant and (mixes and hydration step), removes organic solvent (solvent removal step) then.Therefore, the fine dispersion of colored particles, and thereby can prepare the dispersion of colored particles with excellent storage stability.
Organic solvent must dissolve or disperse dispersant, yet in addition, preferably, described solvent has to a certain degree compatibility to glassware for drinking water.Specifically, the solubility in water is preferably 10～50 quality % under 20 ℃.
More particularly, the colored particles dispersion can prepare by the preparation method who may further comprise the steps (1) and step (2), yet the invention is not restricted to this.
Step (1): to containing pigment, dispersant, can dissolve or disperse the organic solvent of dispersant and alkaline matter and containing the step of carrying out dispersion treatment as the mixture of the water of main component.
Step (2): the step that the mixture after dispersion treatment is removed at least a portion organic solvent.
In step (1), at first, dispersant dissolves in organic solvent or disperses, and forms mixture (blend step).Then, will contain colouring agent and alkaline matter and solution, water and the surfactant when needed etc. that contain as the water of main component are added in the mixture, mixture is mixed and disperses, obtain oil-in-water type colored particles dispersion.
Alkaline matter be used for and polymer in the anionic property group (preferably, carboxyl) that may contain.The degree of neutralization of anionic property group is not particularly limited.Usually, preferred, the liquid properties of the final colored particles dispersion that obtains is for example pH 4.5～10.Can determine the pH value according to the required degree of neutralization of polymer.
The preferred embodiment of organic solvent comprises pure series solvent, ketone series solvent and ether series solvent.Wherein, the example of pure series solvent comprises ethanol, isopropyl alcohol, n-butanol, the tert-butyl alcohol, isobutanol and DAA etc.The example of ketone series solvent comprises acetone, methyl ethyl ketone, metacetone and methyl iso-butyl ketone (MIBK).The example of ether series solvent comprises butyl oxide, oxolane He diox.In these solvents, isopropyl alcohol, acetone and methyl ethyl ketone are preferred, and methyl ethyl ketone is particularly preferred.These organic solvents can use separately or several organic solvent can be used in combination.
When preparation colored particles dispersion, can use twin-roll machine, three-roller, ball mill, rotary screen (throne mill), dispersion machine, kneader, common kneader, homogenizer, agitator, single screw extrusion machine or double screw extruder etc. when applying strong shearing force, to carry out mixing dispersion treatment.In addition, detailed description mixing and that disperse is documented in T.C.Patton, in " Paint Flow and Pigment Dispersion " (1964, John Wiley and Sons, Inc. publication) etc.
In addition, when needed, can use vertical or horizontal sand mill, pin type mill (pin mill), crack grinding machine, ultrasonic dispersing machine etc., use by glass, zirconia etc. and make and particle diameter carries out the differential processing of loosing as the pearl of 0.01mm～1mm, thereby can obtain the colored particles dispersion.
In the method for preparing the colored particles dispersion, the method for removing organic solvent is not particularly limited, and can remove by known method such as decompression distillation and desolvate.
Colored particles in the colored particles dispersion that obtains can keep good dispersity, and the colored particles dispersion that obtains has excellent ageing stability.
According to the present invention, the volume average particle size of colored particles is preferably 10nm～200nm, more preferably 10nm～150nm, more preferably 10nm～100nm again.When volume average particle size is 200nm or more hour, colorrendering quality is satisfactory, and under the situation of ink-jet method, can realize good drop ejection.In addition, when volume average particle size be 10nm or when bigger, light resistance is satisfactory.
The particle diameter of colored particles distributes and is not particularly limited, and can have wide particle diameter distribution or monodispersed particle diameter and distribute.Can also be used in combination and have two or more colored particles that monodispersed particle diameter distributes.
In addition, for example can using, the volume average particle size and the particle diameter of light scattering method measurement colored particles distribute.
According to the present invention, can be used alone colored particles and maybe can be used in combination two or more colored particles.
(water-soluble polymerizable compound)
Ink composite of the present invention contains at least a water-soluble polymerizable compound with at least one polymerizable groups, and can shine and polymerization through active energy beam.
In addition, the term among the present invention " water-soluble " is meant that under 25 ℃, the polymerizable compound of at least 2 quality % is dissolved in the distilled water.Preferably, meltage is at least 5 quality %, and more preferably meltage is at least 10 quality %, and more preferably meltage is at least 20 quality % again, and preferred especially and water is with the mixed uniformly compound of any required ratio.
Polymerizable groups is not particularly limited, as long as it is to shine and the functional group of polymerization through active energy beam, the example comprises vinyl, pi-allyl, (methyl) acryloyl group and its derivative.Wherein, fusible viewpoint from the image that forms, be preferably selected from least a of (methyl) acrylate group, (methyl) acrylamide group, maleimide base group, vinyl sulfone group and N-vinylamide group, more preferably (methyl) acrylamide group.
" (methyl) acrylate " that use among the present invention is meant " acrylate " or " methacrylate " at least.
Polymerizable groups quantity contained in the water-soluble polymerizable compound is not particularly limited.Yet, from the cohesive of the image that forms and the viewpoint of resistance to blocking, preferred 2 or more polymerizable groups, more preferably 2～6, more preferably 2～3 again.
When water-soluble polymerizable compound had at least 2 polymerizable groups, they can be same to each other or different to each other.
From solidifying the viewpoint of sensitivity and resistance to blocking,, preferably, have at least 2 polymerizable functional groups that are selected from (methyl) acrylamide group, maleimide base group and vinyl sulfone group according to the present invention.More preferably, have at least one (methyl) acrylamide group, more preferably have at least 2 (methyl) acrylamide groups again.
Except polymerizable groups, water-soluble polymerizable compound preferably has at least one hydrophilic radical.As hydrophilic radical, any in nonionic group, anionic property group and the cationic group all can use.In addition, can use betaine.
The instantiation of water-soluble polymerizable groups comprises oxyalkylene and its oligomer, hydroxyl, amide group, sugar alcohol residue, urea groups, imino group, amino, carboxyl, sulfonate radical, phosphate radical, thiol group and quaternary ammonium group.
According to the present invention, from the viewpoint of image cohesive, curing sensitivity and resistance to blocking, hydrophilic radical is preferably selected from oxyalkylene and its oligomer, hydroxyl, amide group, sugar alcohol residue, urea groups, imino group, amino, carboxyl, sulfonate radical, phosphate radical and thiol group.More preferably, it is be selected from oxyalkylene and its oligomer and hydroxyl at least a.Again more preferably, it is to be selected from oxygen ethylidene, oxygen propylidene and its oligomer (n=1～2) and hydroxyl is at least a.
When above-mentioned specific polymerizable compound had at least 2 polymerizable groups and also contains hydrophilic radical, the binding form between polymerizable groups and the hydrophilic radical was not particularly limited.Yet,, preferably, have wherein at least 2 polymerizable groups via the form of divalence hydrophilic radical binding at least from solidifying the viewpoint of sensitivity and resistance to blocking.
The example of the described hydrophilic radical of divalence at least comprises wherein at least one hydrogen atom or the removed compound residue of hydroxyl that is selected from following compound.
-compound group-
Polyalcohols, as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propane diols, DPG, tripropylene glycol, polypropylene glycol, 1, ammediol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, 2, the 3-butanediol, 1, the 5-pentanediol, 1, the 4-pentanediol, 2, the 4-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-methyl-2, the 4-pentanediol, 1, the 5-hexylene glycol, 1, the 6-hexylene glycol, 2, the 5-hexylene glycol, glycerine, 1,2, the 4-butantriol, 1,2, the 6-hexanetriol, 1,2,5-penta triol, THIOGLYCOL, trimethylolpropane, two (trimethylolpropanes), trimethylolethane, two (trimethylolethanes), neopentyl glycol, pentaerythrite, dipentaerythritol and its condensation product, low molecular weight polyethylene alcohol or carbohydrate.
The polyamine class is as ethylenediamine, diethylenetriamines, trien, polymine and poly-propane diamine.
Saturated or undersaturated heterocyclic compound is as pyridine, imidazoles, pyrazine, piperidines, piperazine and morpholine.
In addition, from the curing sensitivity of the image that forms and the viewpoint of resistance to blocking, the ratio of the quantity of contained polymerizable groups in its molecular weight of water-soluble polymerizable compound of the present invention and the water-soluble polymerizable compound, promptly, the value of trying to achieve divided by the quantity of polymerizable groups contained in each molecule with the molecular weight of polymerizable compound (molecular weight/polymerizable groups of polymerizable compound contain quantity, below, can be called " A value "), be preferably 175 or littler, more preferably 165 or littler.In addition, from the viewpoint of chemical constitution, the A value is preferably 84 or bigger.
According to the present invention, from solidifying the viewpoint of sensitivity and resistance to blocking, preferably, water-soluble polymerizable compound has at least 2 polymerizable groups that are selected from (methyl) acrylamide group, maleimide base group, vinyl sulfone group and N-vinylamide group, and its A value is 84～175.More preferably, have at least 2 polymerizable groups that are selected from (methyl) acrylamide group, maleimide base group, vinyl sulfone group and N-vinylamide group, its A value is 84～165.More particularly, it is that to have at least 2 (methyl) acrylamide groups and A value be 84～165 compound.
In addition, preferably, to have at least 2 polymerizable groups and the A value that are selected from (methyl) acrylamide group, maleimide base group, vinyl sulfone group and N-vinylamide group and nonionic hydrophilic radical be 84～175 to above-mentioned specific polymerizable compound.More preferably, have at least 2 polymerizable groups that are selected from (methyl) acrylamide group, maleimide base group, vinyl sulfone group and N-vinylamide group, at least a nonionic hydrophilic radical that is selected from oxyalkylene, its oligomer and hydroxyl, and the A value is 84～165.Especially more preferably have at least 2 (methyl) acrylamide groups, be selected from least a nonionic hydrophilic radical of oxyalkylene, its oligomer and hydroxyl, and the A value is 84～165.
The instantiation of water-soluble polymerizable compound of the present invention is shown below, but the invention is not restricted to this.
Figure BSA00000463194400261
Polymerizable compound 1 polymerizable compound 2
Polymerizable compound 3 polymerizable compounds 4
Figure BSA00000463194400263
Polymerizable compound 5 polymerizable compounds 6
Figure BSA00000463194400264
Polymerizable compound 7 polymerizable compounds 8
Figure BSA00000463194400265
Polymerizable compound 9 polymerizable compounds 10
Figure BSA00000463194400266
Polymerizable compound 11 polymerizable compounds 12
Figure BSA00000463194400267
Polymerizable compound 13 polymerizable compounds 14
Figure BSA00000463194400271
Polymerizable compound 15 polymerizable compounds 16
Figure BSA00000463194400272
Polymerizable compound 17 polymerizable compounds 18
Figure BSA00000463194400273
Polymerizable compound 19 polymerizable compounds 20
Figure BSA00000463194400274
Polymerizable compound 21 polymerizable compounds 22
Figure BSA00000463194400275
Polymerizable compound 23 polymerizable compounds 24
Polymerizable compound 25 polymerizable compounds 26
Figure BSA00000463194400282
Polymerizable compound 27 polymerizable compounds 28
Figure BSA00000463194400283
Polymerizable compound 29 polymerizable compounds 30
Figure BSA00000463194400291
Polymerizable compound 31
Figure BSA00000463194400292
Polymerizable compound 32
Polymerizable compound 33
Figure BSA00000463194400294
Polymerizable compound 34
Figure BSA00000463194400301
About water-soluble polymerizable compound of the present invention, except above-mentioned water-soluble polymerizable compound, can also suitably use following water-soluble polymerizable compound.
The example of nonionic polymerisable monomer comprises such as polymerizable compounds such as (methyl) acrylate monomers.The example of (methyl) acrylate monomer comprises ultraviolet hardening monomer and oligomer, as (methyl) acrylate and the polybase acid anhydrides of the epoxy adduct of (methyl) acrylate of (methyl) acrylate of the glycidyl ether of (methyl) acrylate of polyalcohol, polyalcohol, polyethylene glycol, polyalcohol with contain reactant between (methyl) acrylate of hydroxyl.
The internal chain that polyalcohol can have according to the ethylene oxide chain of the adding formation of oxirane prolongs.
The instantiation (nonionic polymerizable compound 1～6) of nonionic polymerizable compound is shown below.Yet, the invention is not restricted to this.
Figure BSA00000463194400321
Nonionic compound 1
Figure BSA00000463194400322
Nonionic compound 2
Figure BSA00000463194400323
Nonionic compound 3
Figure BSA00000463194400324
Nonionic compound 4
Figure BSA00000463194400325
Nonionic compound 5
Figure BSA00000463194400326
Nonionic compound 6
In addition, can also use the acrylate that in a molecule, has at least 2 acryloyl groups that stems from polyol.The example of polyol comprises the condensation product of glycols, as oligo-ether and oligoester.
In addition, the suitable example of nonionic polymerizable compound comprises (methyl) acrylate of the polyalcohol with at least 2 hydroxyls, as monosaccharide and disaccharides; (methyl) acrylate with triethanolamine, diethanol amine, trihydroxy aminomethane or trihydroxy aminoethane.
In addition, can also suitably use the water-soluble polymerizable compound of cationic for the present invention.
The water-soluble polymerizable compound of cationic is the compound with cationic group and polymerizable groups such as unsaturated double-bond, and its embodiment that is fit to comprises epoxy monomer and oxetane monomer.When containing the cationic polymerizable compound, owing to have the cationic grow that the cationic group makes ink composite, the result can more effectively prevent the colour mixture because of using anionic property printing ink to cause.
The example of cationic polymerizable compound comprises N, N-dimethyl amino ethyl methacrylate, N, N-dimethyl amino ethyl acrylate, N, N-dimethylaminopropyl methacrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylamino acrylamide, N, N-dimethylaminomethyl acrylamide, N, N-dimethyl aminoethyl acrylamide, N, N-dimethyl aminoethyl Methacrylamide, N, N-dimethylaminopropyl acrylamide, N, the compound of N-dimethylaminopropyl Methacrylamide and their seasonizations.
The example of epoxy monomer comprises glycidyl ether and the glycidyl esters and the aliphatic cyclic rings oxide of polyalcohol.
In addition, as the example of cationic polymerizable compound, can comprise compound with following structure.
Structure 1 structure 7
Structure 2 structures 8
Figure BSA00000463194400342
Structure 3 structures 9
Structure 4 structures 10
Figure BSA00000463194400344
Structure 5 structures 11
Figure BSA00000463194400345
Structure 6 structures 12
Figure BSA00000463194400346
In said structure, R represents the polyalcohol residue.In addition, X represents H or CH 3, A -Represent Cl -, HSO 3 -Or CH 3COO -The examples for compounds that is used to introduce polyalcohol comprises glycerine, 1,2,4-butantriol, 1,2,5-pentanediol, 1,2,6-hexanetriol, trimethylolpropane, Pehanorm, trimethylolethane, pentaerythrite, bisphenol-A, alicyclic bisphenol-A and their condensation product.
The instantiation (cationic compound 1～11) of the polymerizable compound with cationic group is shown below.
Cationic compound 1
Cationic compound 2
Cationic compound 3 cationic compounds 5
Figure BSA00000463194400353
Cationic compound 4 cationic compounds 6
Cationic compound 7
Figure BSA00000463194400361
Cationic compound 8
Figure BSA00000463194400362
Cationic compound 9
Figure BSA00000463194400371
Cationic compound 10
Figure BSA00000463194400372
Cationic compound 11
Figure BSA00000463194400373
Water-soluble polymerizable compound can use separately or two or more can be used in combination.
Press solid content meter, the content of the water-soluble polymerizable compound in the ink composite of the present invention is preferably 1～50 quality %, more preferably 1～40 quality %, more preferably 1～30 quality %, most preferably 3～20 quality % again.
In addition, from the cohesive of the image that improve to form and wearability and the viewpoint that suppresses stack height, water-soluble polymerizable compound is preferably 1～30 than (that is, water-soluble polymerizable compound/colored particles) by mass ratio with the content of colored particles, and more preferably 3～15.
(polymerization initiator)
Ink composite of the present invention contains at least a polymerization initiator.About polymerization initiator, can use known polymerization initiator and be not particularly limited.As polymerization initiator of the present invention, preferably use Photoepolymerizationinitiater initiater.
The example of operable preferred light polymerization initiator comprises (a) aromatic ketone among the present invention, (b) acylphosphanes compound, (c) aromatic series salt compound; (d) organic peroxide, (e) thio-compounds, (f) six aryl united imidazoles; (g) ketoxime ester compounds; (h) boric acid ester compound, (i) piperazine compound, (j) Metallocenic compound; (k) active ester compound; (l) have the compound of carbon-halogen bond and (m) alkyl ammonium compounds, etc.
The Photoepolymerizationinitiater initiater of record in 65～148 pages that more specifically example comprises " UV Ray Koka Gijutsu " (Kato Kiyomi work, 1989, Technical Information Institute Co., Ltd. distribution).
About the polymerization initiator among the present invention, can use the water-insoluble initator or the water soluble starter that in water, disperse.Yet, preferred water-soluble polymerization initiator.In addition, the term " water-soluble " that uses for polymerization initiator is meant that the solubility under 25 ℃ is at least 0.5 quality % in distilled water.Water-soluble polymerization initiator preferred dissolution degree under 25 ℃ in distilled water is at least 1 quality %, more preferably at least 3 quality %.
According to the present invention, polymerization initiator can use separately or two or more can be used in combination.
The content of contained polymerization initiator is scaled solids content and is preferably 0.1～30 quality % in the aqueous ink composition of the present invention, more preferably 0.5～20 quality %, more preferably 1.0～10.0 quality % again.
In addition, with respect to the above-mentioned polymerizable compound of 100 weight portions, the content of contained polymerization initiator is preferably 0.01～35 mass parts in the aqueous ink composition of the present invention, more preferably 0.1～30 mass parts, more preferably 1～20 mass parts again.In addition, the content of polymerization initiator is meant the total content of polymerization initiator in aqueous ink composition, and the content of polymerizable compound is meant the total content of polymerizable compound in aqueous ink composition.
(water-medium)
Ink composite of the present invention contains water-medium.Water-medium contains water at least, and optional contains at least a organic solvent.
About the water that uses among the present invention, preferred use does not contain the water of ionic impurity, for example, and ion exchange water and distilled water.In addition, the water content in the ink composite can suitably be selected according to desired use.Yet, usually, be preferably 10～95 quality %, more preferably 30～90 quality %.
-organic solvent-
The water-medium that uses among the present invention preferably contains at least a water-miscible organic solvent.When containing water-miscible organic solvent, can obtain drying prevent, wetting or promote the effect of infiltration etc.For preventing drying, solvent can prevent the spray nozzle clogging that is caused by jet that is attached to nozzle and dry printing ink aggegation as anti-drying dose.From preventing drying or promote wetting viewpoint, the water-miscible organic solvent that preferably uses the steam of steaming pressure ratio water to force down.In addition, water-miscible organic solvent can be used as penetration enhancer, strengthens the permeability that printing ink enters paper.
The example of water-miscible organic solvent comprises alkane glycols (polyalcohol), as glycerine, 1,2, and 6-hexanetriol, trimethylolpropane, ethylene glycol or propane diols; Glycitols; Alkyl alcohols with 1～4 carbon atom is as ethanol, methyl alcohol, butanols, propyl alcohol or isopropyl alcohol; And glycol ethers, as the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, the ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, TC, diethylene glycol list n-propyl ether, the glycol monomethyl isopropyl ether, the diethylene glycol monoisopropyl ether, the glycol monomethyl n-butyl ether, the glycol monomethyl n-butyl ether, diethylene glycol list tertbutyl ether, triethylene glycol list ethylether, 1-methyl isophthalic acid-methoxybutanol, propylene glycol monomethyl ether, propane diols list ethylether, propane diols list tertbutyl ether, propane diols list n-propyl ether, the propane diols monoisopropyl ether, DPG, DPGME, dihydroxypropane single-ethyl ether, DPG list n-propyl ether, DPG monoisopropyl ether or tripropylene glycol monomethyl ether.A kind of in these materials can use separately or these materials in two or more can be used in combination.
For preventing drying or promoting wettingly, can use polyalcohols.Examples of polyhydric alcohols comprises glycerine, ethylene glycol, diethylene glycol, triethylene glycol, propane diols, DPG, tripropylene glycol, 1,3-butanediol and 2,3-butanediol.A kind of in these materials can use separately or these materials in two or more can be used in combination.
For promoting infiltration, preferred polyol compound, preferred aliphat glycol.The example of aliphatic diol comprises 2-ethyl-2-methyl isophthalic acid, ammediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1, ammediol, 2-ethyl-1,3-hexylene glycol and 2,2,4-trimethyl-1,3-pentanediol.Wherein, 2-ethyl-1,3-hexylene glycol and 2,2,4-trimethyl-1,3-pentanediol are preferred.
In addition, curling viewpoint takes place from suppress recording medium, water-miscible organic solvent of the present invention preferably contains at least a compound of following structural formula (1) representative.
Structural formula (1)
In structural formula (1), l, m and n represent 1 or bigger integer independently of one another, and satisfy l+m+n=3～15, and l+m+n preferably 3～12, and more preferably 3～10.When l+m+n is 3 or when bigger, can obtain good inhibition and curl.When l+m+n is 15 or more hour, can obtain good ejection.In structural formula (1), AO represents at least a in oxirane (EO) or the expoxy propane (PO), wherein, and preferred propylene oxide group.(AO) l, (AO) m(AO) nIn each AO can be same to each other or different to each other.
The examples for compounds of structural formula (1) representative is shown below.Yet, the invention is not restricted to this.In addition, about example compound, statement " POP (3) glycerin ether " is meant wherein three glycerin ethers that propylene oxide group combines with glycerine altogether, and similar definition also is applicable to other statements.
Figure BSA00000463194400402
In addition, about water-miscible organic solvent of the present invention, from the viewpoint that suppresses to curl and take place, the water-miscible organic solvent of following example also is preferred.
N-C 4H 9O (AO) 4-H (AO=EO or PO, ratio=1 of EO: PO: 1)
N-C 4H 9O (AO) 10-H (AO=EO or PO, ratio=1 of EO: PO: 1)
HO (AO) 40-H (AO=EO or PO, ratio=1 of EO: PO: 3)
HO (AO) 55-H (AO=EO or PO, ratio=5 of EO: PO: 6)
·HO(PO) 3-H
·HO(PO) 7-H
1,2-ethylene glycol
The compound and the content ratio of above-mentioned example compound in the total water solubleness organic solvent of structural formula (1) representative are preferably at least 3 quality %, more preferably at least 4 quality %, more preferably at least 5 quality % again.When content is in above-mentioned scope, can suppress curling, can not cause the stability or the ejection deterioration of printing ink, be preferred therefore.
According to the present invention, water-miscible organic solvent can use separately or two or more can be used in combination.
In addition, the content of water-miscible organic solvent in ink composite is preferably 1～60 quality %, more preferably 5～40 quality %.
(resin particle)
Ink composite of the present invention preferably contains at least a resin particle.By comprising resin particle, ink composite can improve effectively to the cohesive of recording medium and image wearability and resistance to blocking.
In addition, (that is the resin particle of) function, image, described resin particle makes the printing ink tackify by dispersion aggegation or the instabilityization when contacting with the part of the treatment fluid drying of treatment fluid or recording medium preferably to have fixedly ink composite.These resin particles preferably are dispersed in water and at least a organic solvent.
The example of resin particle of the present invention comprises the latex of acrylate, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic acid-styrene resin, butadiene resin, styrene resin, crosslinked acrylate, crosslinked styrene resin, benzoguanamine resin, phenolic resins, silicones, epoxy resin, polyurethane resin, paraffin resin, fluororesin and these resins.The preferred embodiment of resin particle comprises acrylate, acrylic acid-styrene resin, styrene resin, crosslinked acrylate and crosslinked styrene resin.
In addition, the form that resin particle can latex is used.
The weight average molecular weight of resin particle is preferably 10,000～200, and 000, more preferably 100,000～200,000.
In addition, the volume average particle size of resin particle is preferably 1～100nm, more preferably 1～50nm, more preferably 1～25nm again, preferred especially 2～15nm.
The glass transition temperature temperature T g of resin particle is preferably 30 ℃ or higher, and more preferably 40 ℃ or higher, more preferably 50 ℃ or higher again.
Resin particle is preferably 0.1～20 quality % with respect to the addition of printing ink, more preferably 0.1～15 quality %, more preferably 0.1～10 quality % again.
In addition, the particle diameter of thin resin particle distributes and is not particularly limited, and can use to have those that wide particle diameter distributes or monodispersed particle diameter distributes.In addition, can also mix use and have at least two kinds of resin particles that monodispersed particle diameter distributes.
Surfactant
Can contain surfactant when needed according to ink composite of the present invention.Surfactant can be used as surface tension modifier.
As surface tension modifier, compound can be used effectively, in anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant and the beet alkali surface activator any can be used with the structure that in molecule, comprises hydrophilic parts and hydrophobic parts.In addition, above-mentioned dispersant (polymeric dispersant) also can be used as surfactant.
In the present invention,, can preferably use nonionic surfactant from suppressing the viewpoint of the interference between the droplet of ink, in nonionic surfactant, more preferably acetylenediol derivative.
When ink composite contains surfactant (surface tension modifier), from helping utilizing the viewpoint of ink-jet method jet ink composition, preferably, the addition of surfactant makes the surface tension of ink composite can be adjusted to the scope of 20～60mN/m, the addition of surfactant more preferably makes the surface tension of ink composite can be adjusted to 20～45mN/m, more more preferably 25～40mN/m.
The concrete amount of surfactant in ink composite is not particularly limited, and can be to make the amount of surface tension in preferable range.The amount of surfactant is preferably 1 quality % or more, more preferably 1～10 quality %, more preferably 1～3 quality % again.
Other components
Except said components, when needed, ink composite can also contain various additives as other components.
The example of various additives comprises known additives, as ultra-violet absorber, anti-fading agent, mould inhibitor, pH conditioning agent, antirust agent, antioxidant, emulsion stabilizer, antiseptic, defoamer, viscosity modifier, dispersion stabilizer, chelating agent and solid wetting agent.
The example of ultra-violet absorber comprises that benzophenone series ultra-violet absorber, BTA are that ultra-violet absorber, salicylate are that ultra-violet absorber, cyanoacrylate are that ultra-violet absorber and nickel complex salt are ultra-violet absorber.
As anti-fading agent, can use various organic anti-fading agents and metal complex system anti-fading agent.The example of organic anti-fading agent comprises hydroquinones, alkoxyl phenol, dialkoxy phenol, phenol, aniline, amine, indenes, chroman, alkoxyl aniline and heterocyclic compound.The example of metal complex anti-fading agent comprises nickel complex and zinc complex.
The example of mould inhibitor comprises dehydro sodium acetate, Sodium Benzoate, 1-pyrithione sodium-oxide, p-nipagin A, 1,2-benzisothiazole-3-ketone, sodium sorbate and sodium pentachlorophenol.
The content of mould inhibitor in ink composite is preferably 0.02～1.00 quality %.
The pH conditioning agent is not particularly limited, as long as it can be adjusted to desirable value with pH, and does not influence the ink composite that will prepare unfriendly, and can suitably select according to purpose.The example comprises that hydramine (for example, diethanol amine, triethanolamine, 2-amino-2-ethyl-1, ammediols etc.), alkali metal hydroxide (for example, lithium hydroxide, NaOH, potassium hydroxide etc.), ammonium hydroxide class (for example, ammonium hydroxide, quaternary ammonium hydroxide), phosphonium hydroxides and alkali carbonate.
The example of antirust agent comprises acid accumulator sulfite, sodium thiosulfate, thio-diethylene glycol ammonium, diisopropyl ammonium nilrite, pentaerythritol tetranitrate and dicyclohexyl ammonium nitrite.
The example of antioxidant comprises that phenol is that antioxidant (comprising that sterically hindered phenol is an antioxidant), amine are that antioxidant, sulphur are antioxidant and phosphorous antioxidant.
The example of chelating agent comprises sodium ethylene diamine tetracetate, sodium nitrilo triacetate, hydroxyethylethylene diamine tri-acetic acid sodium, diethylenetriamine pentaacetic acid sodium and uramil sodium diacelate.
The rerum natura of-ink composite-
Surface tension (25 ℃) according to ink composite of the present invention is preferably 20mN/m～60mN/m.More preferably, surface tension is 20mN/m～45mN/m, more more preferably 25mN/m～40mN/m.
Use automatic surface tensometer (Ltd. produces for trade name: CBVP-Z, Kyowa Interface Science Co.) under the condition of 25 ℃ of temperature, to measure the surface tension of ink composite.
The viscosity of ink composite according to the present invention under 25 ℃ is preferably 1mPas～10mPas, more preferably 2mPas but less than 8mPas, more preferably 4mPas but less than 7mPas again.
Can use viscosimeter (Ltd. produces for trade name: TV-22, Toki Sangyo Co.) under the condition of 25 ℃ of temperature, to measure the viscosity of ink composite.
Be applied on the recording medium with above-mentioned specific physical property values by having the surface tension in the above-mentioned scope and the ink composite of viscosity, can form image with excellent adhesiveness.
[treatment fluid]
The printing ink group contains at least a agglutinant that can produce aggregation when contacting with ink composite, can also contain other components when needed.
When treatment fluid contains agglutinant, can form image with good quality and excellent anti adhesive.
(agglutinant)
Treatment fluid of the present invention contains the agglutinant of the composition aggegation that makes ink composite.Agglutinant of the present invention is can aggegation (fixing) ink composite when ink composite on the recording medium contacts, and plays the effect of color-fixing agent.For example, treatment fluid has been applied on the specific recording medium of the present invention and has made agglutinant under the state on the recording medium therein, ink composite also can be applied, thereby contact agglutinant, make the component aggegation of ink composite like this, and the component of ink composite is fixed on the recording medium.
The example of component that is used for fixing the component of ink composite comprises acid compound and multivalent metal salt.These components can use separately or two or more are used in combination.
-acid compound-
The suitable example of acid compound comprises the derivative of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetate, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, butanedioic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid, metaphosphoric acid, pyrrolidones formic acid, pyrones formic acid, pyrrole carboxylic acid, furancarboxylic acid, pyridine carboxylic acid, coumaric acid, thiophenic acid, nicotinic acid, these compounds and the salt of these compounds.
Wherein, the acid compound with high water-soluble is preferred.In addition, from by with the fixing viewpoint of printing ink integral body of ink composite reaction, the acid compound that is not more than 3 valencys is that preferably the acid compound of 2～3 valencys is particularly preferred.
Acid compound can use separately or two or more can be used in combination.
Contain at treatment fluid under the situation of acid compound, the pH of treatment fluid (25 ℃) is preferably 0.1～6.8, and more preferably 0.5～6.0, more more preferably 0.8～5.0.
With respect to the gross mass of treatment fluid, the content of acid compound is 40 quality %, more preferably 15～40 quality % at the most preferably.When the content of acid compound was 10～30 quality %, the composition branch of ink composite can more effectively be fixed.
The amount that acid compound is applied on the recording medium is not particularly limited, as long as present in an amount at least sufficient to the aggegation ink composite.From the viewpoint of the fixedly easiness of ink composite, the coating weight of acid compound is preferably 0.1g/m 2～2.0g/m 2, more preferably 0.1g/m 2～1.0g/m 2
-multivalent metal salt-
Multivalent metal salt of the present invention is to contain the compound of divalent metal at least, and as the metal of alkaline-earth metal or zinc family, the example comprises such as Ca 2+, Cu 2+And Al 3+Acetate and oxide Deng metal ion.
According to the present invention, when ink composite is injected on the recording medium that is coated with the treatment fluid that contains multivalent metal salt, by dispersed particles in the reduction ink composite (for example, particles such as the colouring agent of pigment representative or resin particle) dispersion stabilization and increase ink composite overall viscosity can cause the agglutinating reaction of ink composite.For example, having under the situation of faintly acid functional group such as carboxyl in ink composite such as particles such as pigment or resin particles, the dispersion of particle is stablized because of the effect of faintly acid functional group.Yet, according to the interaction of multivalent metal salt, the surface charge on the particle may reduce and dispersion stabilization is reduced.Therefore, from the viewpoint of agglutinating reaction, comprise in the treatment fluid as the multivalent metal salt needs of color-fixing agent divalent at least, that is, and multivalence.From the viewpoint of agglutinating reaction, multivalent metal salt is the multivalent metal salt of the polyvalent metal ion of at least 3 valencys preferably.
From above viewpoint, operable multivalent metal salt preferably is selected from least a of the salt with anionic polyvalent metal ion, poly-aluminium hydroxide and polyaluminium chloride in the treatment fluid of the present invention.
The example of multivalent metal salt comprises Ca 2+, Cu 2+, Ni 2+, Mg 2+, Sr 2+, Zn 2+, Ba 2+, Al 3+, Fe 3+, Cr 3+, Co 3+, Fe 2+, La 3+, Nd 3+, Y 3+And Zr 4+In order in treatment fluid, to comprise polyvalent metal ion, can use above-mentioned multivalent metal salt.
Salt is meant by above-mentioned polyvalent metal ion and the slaine that can form with the anion of this ions binding.Preferably in solvent soluble those.Here, solvent is meant the medium that forms treatment fluid with multivalent metal salt.The example comprises water and organic solvent described later.
The anionic preferred embodiment that forms salt with polyvalent metal ion comprises Cl -, NO 3 -, I -, Br -, ClO 3 -, CH 3COO -And SO 4 2-
Polyvalent metal ion and anion can form and contain one or more polyvalent metal ions and anionic salt respectively.
The example of the multivalent metal salt outside above-mentioned comprises poly-aluminium hydroxide and polyaluminium chloride.
From reactivity, coloring, the easy viewpoint of property handled etc., preferably use polyvalent metal ion and anionic salt among the present invention.About polyvalent metal ion, be preferably selected from Ca 2+, Mg 2+, Sr 2+, Al 3+And Y 3+At least a, more preferably Ca 2+
In addition, about anion, from the viewpoint of dissolubility etc., NO 3 -Be particularly preferred.
Multivalent metal salt can use separately or two or more can be used in combination.
With respect to the gross mass of treatment fluid, the content of multivalent metal salt is at least 15 quality %.When the content of multivalent metal salt during at least 15 quality %, can be more effectively the fixing component of ink composite.
With respect to the gross mass of treatment fluid, the content of multivalent metal salt is preferably 15～35 quality %, more preferably 20～30 quality %.
The amount that multivalent metal salt is applied on the recording medium is not particularly limited, as long as present in an amount at least sufficient to the aggegation ink composite.Yet from the viewpoint of the fixedly easiness of ink composite, the coating weight of multivalent metal salt is preferably 0.5g/m 2～4.0g/m 2, more preferably 0.9g/m 2～3.75g/m 2
Embodiment
Below in conjunction with the more particularly bright the present invention of embodiment, yet the invention is not restricted to following examples, only otherwise exceed purport of the present invention.Except as otherwise noted, " part " and " % " all by mass.
＜preparation recording medium 1 〉
[preparation ground floor (following coating) coating fluid]
Titanium dioxide (the trade name: TIPAQUE R-780 of mixing 100 parts, Ishihara Industry, Co., Ltd. production), the sodium salt (trade name: DEMOL EP of 1.2 parts 25% special polycarboxylic acid type polymer, Kao Corp. produces) and 121.7 parts water, non-foaming mixing roll (trade name: NBK-2, Nippon Seiki Co. used, Ltd. produce) dispersed mixture, therefore obtain containing the dispersion liquid of 45% titanium dioxide.
Next, to 100 parts 35% styrene-butadiene latexes (MFT: 0 ℃, trade name: NIPOL LX110, Nippon Zeon Co., Ltd. produce) in, add 100 parts water and 3.9 parts the dispersion liquid that contains 45% titanium dioxide that obtains, fully mix, the mixed liquor liquid temperature that obtains remains on 15 ℃～25 ℃, thereby obtains the coating coating fluid 18.0% time.
[the preparation second layer (going up coating) coating fluid]
Powdered whiting (the trade name: ESCALON#2000 of mixing 60 parts, Sankyo Seifun Co., Ltd. production), 20 parts kaolin (trade name: MIRAGLOSS, Engelhard Corporation, U.S. production), 20 parts titanium dioxide (TIPAQUE R-780, Ishihara Industry, Co., Ltd. produce) and 0.5 part 43% Sodium Polyacrylate (trade name: ARON T-50, Toagosei Co., Ltd. produces), the preparation mixture, use Nippon Seiki Co. then, the NBK-2 (trade name) that Ltd produces disperses in water.In dispersion liquid, the average grain diameter that adds 11 parts is the SB latex (trade name: SMARTEX PA2323, Nippon A﹠amp of 95nm; L Inc. production), 3 parts oxidized starch (trade name: ACE B, Oji Cornstarch Co., Ltd. produce) and 1 part lubricant (trade name: SN COAT 231SP, Sun Nopco Co.Ltd. production), obtain final solids content concn like this and be 65% last coating coating fluid.
[forming ground floor (following coating)]
At basic weight is 81.4g/m 2The two sides of high quality paper (Ltd. produces for trade name: SHIRAOI, Nippon Paper Industries Co.) on, the following coating coating fluid that uses the doctor knife coater coating to obtain makes that the coating weight on each face is 10.0g/m 2, with each coated face 50 ℃ dry 3 minutes down, thereby form coating down.The thickness of the following coating that forms in this is 9.4 μ m in stage.
[forming the second layer (going up coating)]
Under being formed with, on the two sides of the high quality paper of coating, use high speed blade coating machine (Ltd. produces for trade name: PM-9040M, SMT Co.) the last coating coating fluid that coating makes, make that the dry mass on each face is 10g/m 2, with each coated face under 150 ℃ of temperature and wind speed 20m/sec dry 3 seconds, go up coating thereby form, obtain recording medium 1.In this case, the thickness of each face of coating is 9.5 μ m in this stage formation.
＜preparation recording medium 2 〉
[preparation ground floor (following coating) coating fluid]
With kaolin (trade name: KAOBRITE 90, Shiraishi Calcium Kaisha, Ltd. production) 100 parts, 0.1mol/L NaOH (Wako Pure Chemical Industries, Ltd. production) 3.8 parts, 40% Sodium Polyacrylate (trade name: ARON P50, Toagosei Co., Ltd. production) 1.3 parts mix for 49.6 parts with water, with the mixture that obtains with non-foaming mixing roll (trade name: NBK-2, NipponSeiki Co., Ltd. produce) disperse, thus make 65% kaolin dispersion.Then, with 5 parts in 7.0 parts of 65% kaolin dispersions, water and the 10%EMULGEN 109P (trade name that makes like this, Kao Corp. produces) 0.8 part be added to 22.5% waterborne polyester polyurethane rubber latex dispersion (glass transition temperature: 49 ℃, MFT: 29 ℃; Trade name: HYDRANAP-40F (trade name), Dainippon Ink and Chemicals, Inc. produces) in 100 parts, fully stir then and mix.The liquid temperature of the liquid mixture that obtains is like this remained on 15 ℃～25 ℃, obtain the coating coating fluid 24.0% time.
[the preparation second layer (going up coating) coating fluid]
With kaolin (trade name: KAOBRITE 90, Shiraishi Calcium Kaisha, Ltd. production) 100 parts, 0.1N NaOH (Wako Pure Chemical Industries, Ltd. production) 3.8 parts, 40% Sodium Polyacrylate (trade name: ARON T-50, Toagosei Co., Ltd. production) 1.3 parts mix for 49.6 parts with water, with the mixture that obtains with non-foaming mixing roll (trade name: NBK-2, Nihonseiki Kaisha Ltd. produces) disperse, thus make 65% kaolin dispersion.Then, with average grain diameter is the 50% SB latex (trade name: NIPOL LX407K of 130nm, Zeon Corporation production) 14 parts, the emulsion of fatty acid calcium (trade name: NOPCOAT C-104-HS, San Nopco Limited production) 1 part, 1% sanlose (trade name: SEROGEN EP, Dai-ichi Kogyo Seiyaku Co. production) 10 parts and the 10%EMULGEN 109P aqueous solution (trade name, Kao Corp. produces) 0.5 part be added in the dispersion, be 59% last coating coating fluid thereby make final solids content.Last its shear viscosity of coating coating fluid that makes like this is 50.2mPas～138.2mPas.
[forming coating down]
At basic weight is 81.4g/m 2Each face on two sides of high quality paper (trade name: SHIRAOI, Nippon Paper Co. produce) on, the following coating coating fluid that uses the doctor knife coater coating to make above makes that the coating weight on each face is 8.0g/m 2,, thereby form coating down then at 70 ℃ of following dry 3min.The thickness of following coating is 8.1 μ m.The following coating of such formation is carried out following soft calendering again to be handled.
-soft calendering processing-
The soft calender that use has pair of metal roller and resin roll carries out soft calendering processing to the high quality paper of coating under being formed with on the surface under the following conditions: the surface temperature of metallic roll is 50 ℃, and clamp pressure (nip pressure) is 50kg/cm.
[forming the second layer (going up coating)]
Under being formed with, on the two sides of the high quality paper of coating, use high speed blade coating machine (Ltd. produces for trade name: PM-9040M, SMT Co.) the last coating coating fluid that coating makes, make that the dry mass on each face is 20g/m 2,, go up coating thereby form with each coated face under 150 ℃ of temperature and wind speed 20m/sec dry 3 seconds.In this case, the thickness of each face of coating is 19.1 μ m in this stage formation.In addition, handle, obtain recording medium 2 by on the following coating that forms, carrying out soft calendering.
-soft calendering processing-
The soft calender that use has pair of metal roller and resin roll carries out soft calendering processing to the high quality paper that is formed with coating on the surface under the following conditions: the surface temperature of metallic roll is 50 ℃, and clamp pressure is 50kg/cm.
＜preparation recording medium 3 〉
By preparing recording medium 3 with preparation recording medium 1 same way as, it is as follows that difference is that " preparation down coating coating fluid " and " forming coating down " changes, and in preparation recording medium 1 in the formation on each face of coating on the coating weight of coating coating fluid become 10.8g/m 2Here, the thickness of the following coating of Xing Chenging is 8.0 μ m like this, and the thickness of the last coating of Xing Chenging is 11.0 μ m like this.
[preparation ground floor (following coating) coating fluid]
(1) preparation poly-vinyl alcohol solution
12 parts polyvinyl alcohol (saponification degree: 98.5%, the degree of polymerization: 1,700, trade name: PVA-117, Kuraray Co., Ltd. produces) are added in 88 parts the water, and under 90 ℃ or higher temperature stirring and dissolving.
(2) hydroexpansivity mica dispersion (the ratio of width to height: 1,000, trade name: SOMASIF MEB-3 (8% solution), Co-op Chemical Co.Ltd. produce, average grain diameter is the mica dispersion of 2.0 μ m).
(3) oxirane surfactant (Ltd. produces for trade name: EMALEX 710, Nihon-Emulsion Co.) 1.66% solution (in methyl alcohol, dissolving).
The water that in 100 parts 12% poly-vinyl alcohol solution (1), adds 58 parts, fully stir and mixing, to the 8% hydroexpansivity mica dispersion liquid (2) that wherein adds 18 parts, fully stir and mix, to the 1.66% oxirane surfactant solution (3) that wherein adds 3 parts.The liquid temperature of the mixed liquor that obtains remains on 30 ℃～35 ℃, obtains down the coating coating fluid.
[forming ground floor (following coating)]
At basic weight is 81.4g/m 2Each face on two sides of high quality paper (trade name: SHIRAOI, Nippon Paper Co. produce) on, the following coating coating fluid that uses the doctor knife coater coating to make above makes that the coating weight on each face is 8.0g/m 2,, thereby form coating down then at 50 ℃ of following dry 3min.
＜preparation recording medium 4 〉
By preparing recording medium 4 with preparation recording medium 1 same way as, it is as follows that difference is that " preparation down coating coating fluid " changes, and under in preparation recording medium 3, forming the following coating coating fluid on each face of coating coating weight and form on each face of coating on the coating weight of coating coating fluid become 5.0g/m respectively 2And 10.1g/m 2Here, the thickness of the following coating of Xing Chenging is 5.2 μ m like this, and the thickness of the last coating of Xing Chenging is 9.9 μ m like this.
[preparation ground floor (following coating) coating fluid]
(1) preparation acetoacetyl modified polyethylene alcohol
Acetoacetyl modified polyethylene alcohol (saponification degree: 95～97% with 12 parts; the degree of polymerization: 1; 000; trade name: GOHSEFIMER Z-210; The Nippon Synthetic Chemical Industry Co.; Ltd. produce) be added in 88 parts the water, and under 90 ℃ or higher temperature stirring and dissolving.
(2) hydroexpansivity mica dispersion (the ratio of width to height: 1,000, trade name: SOMASIF MEB-3 (8% solution), Co-op Chemical Co.Ltd. produce, average grain diameter is the mica dispersion of 2.0 μ m).
(3) oxirane surfactant (Ltd. produces for trade name: EMALEX 710, Nihon-Emulsion Co.) 1.66% solution (in methyl alcohol, dissolving).
In 100 parts 12% acetoacetyl modified polyethylene alcoholic solution (1); the water that adds 58 parts; fully stir and mixing; to the 8% hydroexpansivity mica dispersion liquid (2) that wherein adds 18 parts; fully stir and mixing; to the 1.66% oxirane surfactant solution (3) that wherein adds 3 parts, fully mix then.Then,, add 15.0 parts 40% glyoxal water solution, and fully mix as curing agent solution.The liquid temperature of the mixed liquor that obtains remains on 30 ℃～35 ℃, obtains down the coating coating fluid.
＜preparation recording medium C1～C3 〉
With reference to the comparative example 1～3 of record in paragraph [0249]～[0251] of JP-A No.2009-73158, preparation recording medium C1～C3.
The evaluation of＜recording medium 〉
On the recording medium that obtains, carry out " being formed with the Cobb absorption of water test of the high quality paper of coating down on it " and " going up the water absorption test of coating " in the above, as follows.The results are shown in the table 1.
-Cobb absorption of water the test of the high quality paper of coating under being formed with on it-
(1), measures the Cobb absorption of water (water infiltration capacity (g/m when contacting 15 seconds of the coated face of the high quality paper of coating under being formed with on it with 20 ℃ of water according to the absorption of water method of testing of JIS P8140 regulation 2)).
(2), measure the Cobb absorption of water (water infiltration capacity (g/m when contacting 2 minutes of the coated face of the high quality paper of coating under being formed with on it with 20 ℃ of water according to the absorption of water method of testing of JIS P8140 regulation 2)).
(3), measure the Cobb value (diethylene glycol infiltration capacity (g/m when contacting 2 minutes of the coated face of the high quality paper of coating under being formed with on it with 20 ℃ of diethylene glycols according to the absorption of water method of testing of JIS P8140 regulation 2)).
-upward water absorption the test of coating-
Measure based on following Bristow method.
(1) the last coating sample that will be cut into the A6 size is placed on the measurement dish, and the head that is filled with test fluid (water) is contacted with sample surfaces, and direction from inside to outside is along helical scanning line automatic scan sample surfaces, thereby measures the absorbency of sample.Rotary speed (time of contact between paper and the printing ink) by progressively changing the measurement dish obtains the relation between time of contact and the liquid absorption (water absorption).Table 1 shows the water absorption of 0.5 second time of contact.
(2) measure by the mode similar to said method (1), difference is that test fluid (water) of using in (1) becomes the pure water that contains 30 quality % diethylene glycols (water/DEG).Table 1 shows the liquid absorption of 0.9 second time of contact.
[table 1]
Figure BSA00000463194400521
[preparation ink composite]
(synthetic water insoluble polymer dispersant P-1)
The 88g methyl ethyl ketone is placed the 1000mL three-neck flask that is equipped with agitator and cooler, in nitrogen atmosphere, be heated to 72 ℃.In 3 hours, pass through dissolving 0.85g 2 in the 50g methyl ethyl ketone, the solution that 2 '-azo-bis-iso-dimethyl, 50g methacrylic acid phenoxy group ethyl ester, 13g methacrylic acid and 37g methyl methacrylate obtain to wherein dripping.After being added dropwise to complete, mixture reacted 1 hour again, added then by dissolving 0.42g 2 in the 2g methyl ethyl ketone, the solution that 2 '-azo-bis-iso-dimethyl obtains.Temperature was raised to 78 ℃, with mixture heating 4 hours.The reaction solution that obtains precipitates twice with excessive greatly hexane, with the resin drying that is settled out, obtain 96.5g methacrylic acid phenoxy group ethyl ester/methyl methacrylate/methacrylate (copolymerization ratio [quality % ratio]=50/37/13) copolymer (pitch dispersant P-1).
By 1The composition of the pitch dispersant P-1 that the H-NMR affirmation obtains, the weight average molecular weight of determining by GPC (Mw) is 49,400.In addition, determine acid number by the method for record in the JIS standard (JIS K0070:1992), acid number is 84.8mgKOH/g.
In addition, use gel permeation chromatography (GPC) to measure weight average molecular weight.The HLC-8220GPC (trade name) that uses Tosoh Corp. to produce is used for GPC, three posts that are connected in series: TSK gel Super HZM-H, TSK gel Super HZ4000 and TSK gel Super HZ2000 (trade name is produced by Tosoh Corp.).The eluant, eluent that uses is THF (oxolane).About condition, sample concentration is 0.35%, and flow velocity is 0.35ml/min, and the sample injection rate is 10 μ l, and measuring temperature is 40 ℃, uses the RI detector.From following 8 " standard sample TSK standard, polystyrene " sample making calibration curve: " F-40 ", " F-20 ", " F-4 ", " F-1 ", " A-5000 ", " A-2500 ", " A-1000 " and " n-propylbenzene " (trade name, Tosoh Corp. produces).
(preparation colored particles dispersion C)
Mix 10 parts Pigment Blue (Phthalocyanine Blue A220, trade name, Dainichi Seka Co., Ltd. production in 15: 3; Green pigment), 4 parts polymeric dispersant P-1,44 parts methyl ethyl ketone, 4.4 parts the 1mol/LNaOH aqueous solution and 85.2 parts ion exchange water, use the ball mill of zirconium oxide bead that mixture was disperseed 2 hours to 6 hours with diameter 0.1mm.
From the dispersion that obtains, methyl ethyl ketone is removed in decompression under 55 ℃, removes a part of water again.Then, use high speed Refrigerated Centrifuge 7550 (trade name, Kubota Corp. produces) and use the 50mL centrifuge tube under 8000rpm, to carry out centrifugal 30 minutes, reclaim the supernatant outside the precipitation.Then, determine pigment concentration, obtain colored particles dispersion C like this from absorption spectrum, as the dispersion of resin-coated granules of pigments (pigment of sealing), pigment concentration 10.2 quality %.
(preparation is from dispersed polymeres particle (example compound B-01))
The 360.0g methyl ethyl ketone is placed the 2L three-neck flask that is equipped with agitator, thermometer, reflux condenser and nitrogen ingress pipe, and temperature rises to 75 ℃.When flask interior remains on 75 ℃ of temperature, with 180.0g acrylic acid phenoxy ethyl, 162.0g methyl methacrylate, 18.0g acrylic acid, 72g methyl ethyl ketone and 1.44g " V-601 " (trade name, Wako Pure Chemical Industries, Ltd. mixed solution production) is added drop-wise in the flask with constant rate of speed, drips and finishes in 2 hours.After finishing dropping, add the solution of 0.72g " V-601 " and 36.0g methyl ethyl ketone, mixture stirred 2 hours down at 75 ℃.The solution that adds 0.72g " V-601 " and 36.0g methyl ethyl ketone again stirs mixture 2 hours down at 75 ℃., temperature risen to 85 ℃, continue to stir 2 hours, obtain the resin solution of acrylic acid phenoxy ethyl/methyl methacrylate/acrylic acid (=50/45/5[mass ratio]) copolymer thereafter.
The weight average molecular weight (Mw) of the copolymer that measures with above-mentioned same way as is 64,000 (by above-mentioned gel permeation chromatography (GPC), being scaled value of polystyrene).Acid number is 38.9mgKOH/g
Then, the resin solution that weighing 668.3g obtains adds the 388.3g isopropyl alcohol and the 145.7ml1mol/L NaOH aqueous solution in resin solution, and the temperature in the reaction vessel is raised to 80 ℃.Then, the speed with 20ml/min drips 720.1g distilled water, the formation water-borne dispersions in reaction vessel.Under 80 ℃ of reaction vessel interior temperature, under atmospheric pressure mixture was placed 2 hours, placed 2 hours down at 85 ℃ then, placed 2 hours down at 90 ℃ then.Then, with the reaction vessel interior decompression, remove isopropyl alcohol, methyl ethyl ketone and distilled water that total amount is 913.7g.As a result, obtain the aqueous dispersion from dispersed polymeres particle (example compound B-01), solid concentration is 28.0 quality %.
(preparation ink composition for ink jet)
-preparation ink composite C-1-
The granules of pigments dispersion C that mixing obtains above and from dispersed polymeres particle (example compound B-01) and polymerizable compound 1 obtains following printing ink and forms.In its plastics disposable syringe of packing into, filter by 5 μ mPVDF filters (Millipore Corp. produces for MILLEX-SV (trade name), diameter 25mm), obtain cyan ink (ink composition for ink jet) C-1.
The DV-III ULTRA CP (trade name) that uses Brookfield Engineering Labs. to produce measures the viscosity (25 ℃) of the cyan ink C-1 that obtains like this, and viscosity is 4.2mPas.
-ink composite-
Colored particles dispersion C 29.4%
Aqueous dispersion (B-01) (solids content) 1% from dispersed polymeres particle
Water-soluble polymerizable compound (showing polymerizable compound 1 down) 22%
SUNNIKS GP-250 (trade name) 1.5%
(Sanyo ChemicalIndustries, Ltd. produces)
Olfine E1010 (trade name: Nissin Chemical Industry Co., Ltd. produces)
1％
IRGACURE2959 (trade name: Ciba Inc. produces) 3.3%
Ion-exchange water surplus (being added to total amount 100 quality %)
-preparation ink composite C-2～C-9-
Prepare ink composite C-2～C-9 respectively by mode same as described above, difference is by using the water-soluble polymerizable compound shown in the following table 2 to replace to be used to the polymerizable compound 1 for preparing ink composite C-1 to change the content ratio.
In addition, polyethyleneglycol diacrylate (Ltd. produces for trade name: A-400, Shin Nakamura Chemical Co.) is as polymerizable compound 31.
-preparation ink composite C-10-
Prepare ink composite C-10 by mode same as described above, difference is not add the polymerizable compound 1 that is used to prepare ink composite C-1.
Figure BSA00000463194400551
Polymerizable compound 1 polymerizable compound 2
Figure BSA00000463194400552
Polymerizable compound 3 polymerizable compounds 4
Figure BSA00000463194400553
Polymerizable compound 5 polymerizable compounds 6
Figure BSA00000463194400554
Polymerizable compound 22
(preparation treatment fluid 1)
Mix and have each component of following composition, preparation treatment fluid 1.The viscosity of treatment fluid, surface tension and pH (25 ℃) are as follows: viscosity 2.5mPas, and surface tension 40mN/m, pH 1.0.Use full-automatic surface tensiometer (trade name: CBVP-Z tensiometer, Kyowa Interface Science Co., Ltd. production) surface tension.The DV-IIIULTRA CP (trade name) that uses Brookfield Engineering Labs. to produce measures viscosity.The pH meter HM-30R (trade name) that uses DKK-TOA Corporation to produce measures pH.
The composition of-treatment fluid 1-
Malonic acid (Wako Pure ChemicalIndustries, Ltd. produces) 12.5%
Malic acid (Wako Pure ChemicalIndustries, Ltd. produces) 12.5%
Diethylene glycol single-butyl ether (Wako Pure ChemicalIndustries, Ltd. produces)
20.0％
·EMULGEN?109P 1.0％
(trade name: Kao Corporation produces, nonionic surfactant)
Ion exchange water 54%
＜embodiment 1～embodiment 13 and comparative example 1～comparative example 4 〉
(formation of image and evaluation)
Have shown in the following table 2 treatment fluid that obtains above 1, recording medium and the ink composite of combination by use, the following formation of carrying out image and evaluation (that is, curl, fold and cohesive).Evaluation result is shown in the following table 2.
Prepare 1, the piezoelectricity solid line ink gun of 200dpi/20 inch width, the storagetank that the ink composite that obtains is above packed into and is connected with ink gun.Recording medium is fixed to 500mm/sec on the platform that predetermined rectilinear direction moves, and platform temperature remains on 30 ℃.Use doctor knife coater to be coated with the treatment fluid 1 that obtains above, obtain the thickness of about 1.2 μ m, following dry 2 seconds at 50 ℃ immediately after the coating.
, be provided with and fixedly ink gun, make the orientation (main scanning direction) of nozzle of linear head form 75.7 ° angle with the direction of platform moving direction (sub scanning direction) orthogonal thereafter.When, spraying with linear mode with the constant speed movable recording media time at sub scanning direction, injection conditions is: every quantity of ink is that 2.8pL, injection frequency are 25.5kHz, resolution ratio is 1,200dpi * 1,200dpi, the maximum adding quantity of ink composite are 8.5ml/m 2Thereafter, on the whole surface of the recording medium sample that is cut into the A5 size, ink jet forms solid-state image.Behind document image, use the IR heater to heat, and use air blast to carry out drying 15 seconds with the hot blast of 120 ℃ of 5m/sec supplies from the phase dorsal part (dorsal part) of printing ink coated side.Behind dry image, irradiation ultraviolet radiation (metal halide lamp that Eye Graphics Co.Ltd. produces, maximum illumination wavelength 365nm), to cumulative exposure be 3000mJ/cm 2Thereby, image is solidified.
[evaluation of curling]
For solid-state image sample in measurement sample curvature C, it is prepared to size 5mm * 50mm, makes to form arcuation in curling duration side.
-curvature measurement method-
Under the environmental condition of 25 ℃ of relative humidity 50%, temperature to utilize the sample curvature C after ink jet recording liquid forms image to measure by said method.In addition, be the circular arc of diameter R if curl, then crimp values is represented with following formula 1.
C=1/R (m) (formula 1)
-evaluation criterion-
A: form image after 10 minutes, sample curvature C is not more than 20.
B: form image after 1 day, sample curvature C is not more than 20.
C: be coated with after 7 days, sample curvature C is not more than 20.
D: be coated with after 7 days, C is greater than 20 for sample curvature.
[evaluation of fold]
Use scribbles the recording medium of the postcard size of coating, and the printing size is the 100% monochromatic solid image of 10cm * 1.5cm in medium central authorities.After forming image, under the environmental condition of 35 ℃ of relative humidity 80%, temperature, placed 1 hour.Use the maximum height of the fluctuation that laser displacement sensor (Keyence Corporation productions) measurement takes place under the environmental condition of 25 ℃ of relative humidity 50%, temperature thereafter.
-evaluation criterion-
A: less than 2mm
B:2mm is above but less than 4mm
More than the C:4mm
[fusible evaluation]
In the solid-state image portion that makes according to said method, form image after 2 days, coating CELLOTAPE (registration mark), and peel off immediately, thereby utilize perusal to estimate the extent of exfoliation of the image that forms.Evaluation criterion is as follows, carries out the level Four evaluation according to extent of exfoliation.
-evaluation criterion-
A: do not find fully to peel off.
B: image unconfirmed is peeled off, yet, peel off observe on the adhesive surface of band atomic little painted.
C: show atomic little blank in the image portion, and peel off observe on the adhesive surface of band painted.
D: according to perusal obviously the image portion of visible white point shape peel off, corresponding to can not practical level.
[table 2]
As can be seen from Table 2, according to image forming method of the present invention, curl and being suppressed of fold, thereby form the image that recording medium is had excellent adhesiveness.
The present invention includes following example embodiment.
＜1〉image forming method, it comprises:
By on recording medium, spraying the ink composite that contains colored particles, water-soluble polymerizable compound, polymerization initiator and water, be coated with printing ink and form image, in described recording medium body paper, contain the ground floor of binding agent and contain the second layer stacked above one another of Chinese white, on the surface that is configured in the ground floor on the described body paper, be 5.0g/m with the Cobb absorption of water of measuring 15 seconds time of contact according to the absorption of water test 2Or littler, be 2mL/m according to the Bristow method with the water absorption of measuring time of contact of 0.5 second on the surface of the second layer 2～8mL/m 2
＜2〉as＜1〉described image forming method, wherein said water-soluble polymerizable compound comprises at least 2 polymerizable functional groups that are selected from (methyl) acrylamide group, maleimide base group, vinyl sulfone group and N-vinylamide group.
＜3〉as＜1〉or＜2〉described image forming method, at least one in the wherein said polymerizable functional group is (methyl) acrylamide group.
＜4〉as＜1 〉～＜3 in each described image forming method, to measure 2 minutes time of contact, be 2.0g/m according to absorption of water test in the lip-deep Cobb absorption of water that is configured in the ground floor on the described body paper 2Or it is littler.
＜5〉as＜1 〉～＜4 in each described image forming method, wherein use diethylene glycol to replace water to measure 2 minutes time of contact according to absorption of water test, be 5.0g/m in the lip-deep Cobb value that is configured in the ground floor on the described body paper 2Or littler, and use the water of the diethylene glycol that contains 30 quality % to measure with 0.9 second time of contact according to the Bristow method, the lip-deep liquid absorption of the second layer is 1mL/m 2～6mL/m 2
＜6〉as＜1 〉～＜5 in each described image forming method, the binding agent in the wherein said ground floor comprises thermoplastic resin.
＜7〉as＜6〉described image forming method, wherein said thermoplastic resin comprises polyester-polyurethane latex or acrylic acid silicone latex.
＜8〉as＜1 〉～＜7 in each described image forming method, wherein except described binding agent, described ground floor also comprises layered inorganic compound.
＜9〉as＜1 〉～＜8 in each described image forming method, wherein said binding agent comprises polyvinyl alcohol or acetoacetyl modified polyethylene alcohol.
＜10〉as＜9〉described image forming method, wherein said ground floor comprises at least a following compound as curing agent: the aldehyde based compound; 2,3-dihydroxy-1,4-diox and its derivative; With in a molecule, have at least 2 contiguous Hammett substituent constant σ pCompound for positive substituent vinyl.
＜11〉as＜1 〉～＜10 in each described image forming method, the Chinese white in the wherein said second layer comprises the mixture of kaolin, titanium dioxide or kaolin and titanium dioxide.
＜12〉as＜1 〉～＜11 in each described image forming method, the laminar surface pH in the wherein said second layer is less than 8.0.
＜13〉as＜1 〉～＜12 in each described image forming method, wherein said ink composite comprises the water-soluble polymerizable compound of 3%～20 quality %.
＜14〉as＜1 〉～＜13 in each described image forming method, wherein in described ink composite, described water-soluble polymerizable compound counts 1～30 than (that is water-soluble polymerizable compound/colored particles) by mass ratio with the content of described colored particles.
＜15〉as＜1 〉～＜14 in each described image forming method, the viscosity of wherein said ink composite (25 ℃) is 1～10mPas.
＜16〉as＜1 〉～＜15 in each described image forming method, wherein when described ink composite comprises pigment as described colored particles, comprise the insoluble polymer dispersant as dispersant.
＜17〉as＜16〉described image forming method, wherein said insoluble polymer dispersant comprises having the polyvinyl of carboxyl as the hydrophilic structure unit.
＜18〉as＜1 〉～＜17 in each described image forming method, wherein said ink composite comprises at least a resin particle.
＜19〉as＜1 〉～＜18 in each described image forming method, wherein coating during printing ink the maximum adding quantity of described ink composite be 3～20ml/m 2
＜20〉as＜1 〉～＜19 in each described image forming method, it also comprises:
With cumulative exposure is 10～5000mJ/cm 2Active energy beam irradiation be applied to ink composite on the recording medium.
All publications, patent application and the technical standard mentioned in this specification are all quoted and are incorporated among the application, and its degree just looks like that each publication, patent application or technical standard are all quoted particularly and individually and incorporated among the application.

Claims (20)

1. image forming method, it comprises:
By on recording medium, spraying the ink composite that contains colored particles, water-soluble polymerizable compound, polymerization initiator and water, be coated with printing ink and form image, in described recording medium body paper, contain the ground floor of binding agent and contain the second layer stacked above one another of Chinese white, on the surface that is configured in the described ground floor on the described body paper, be 5.0g/m with the Cobb absorption of water of measuring 15 seconds time of contact according to the absorption of water test 2Or littler, be 2mL/m according to the Bristow method with the water absorption of measuring time of contact of 0.5 second on the surface of the second layer 2～8mL/m 2
2. image forming method according to claim 1, wherein said water-soluble polymerizable compound comprise at least 2 polymerizable functional groups that are selected from (methyl) acrylamide group, maleimide base group, vinyl sulfone group and N-vinylamide group.
3. image forming method according to claim 1, at least one in the wherein said polymerizable functional group are (methyl) acrylamide groups.
4. image forming method according to claim 1 according to the time of contact measurement of absorption of water test with 2 minutes, is 2.0g/m in the lip-deep Cobb absorption of water that is configured in the described ground floor on the described body paper wherein 2Or it is littler.
5. image forming method according to claim 1, wherein test uses diethylene glycol to replace water to measure 2 minutes time of contact according to absorption of water, is 5.0g/m in the lip-deep Cobb value that is configured in the described ground floor on the described body paper 2Or littler, and use the water of the diethylene glycol that contains 30 quality % to measure with 0.9 second time of contact according to the Bristow method, the lip-deep liquid absorption of the described second layer is 1mL/m 2～6mL/m 2
6. image forming method according to claim 1, the binding agent in the wherein said ground floor comprises thermoplastic resin.
7. image forming method according to claim 6, wherein said thermoplastic resin comprise polyester-polyurethane latex or acrylic acid silicone latex.
8. image forming method according to claim 1, wherein except described binding agent, described ground floor also comprises layered inorganic compound.
9. image forming method according to claim 1, wherein said binding agent comprise polyvinyl alcohol or acetoacetyl modified polyethylene alcohol.
10. image forming method according to claim 9, wherein said ground floor comprise at least a following compound as curing agent: the aldehyde based compound; 2,3-dihydroxy-1,4-diox and its derivative; With in a molecule, have at least 2 contiguous Hammett substituent constant σ pCompound for positive substituent vinyl.
11. image forming method according to claim 1, the Chinese white in the wherein said second layer comprises the mixture of kaolin, titanium dioxide or kaolin and titanium dioxide.
12. image forming method according to claim 1, the laminar surface pH in the wherein said second layer is less than 8.0.
13. image forming method according to claim 1, wherein said ink composite comprise the described water-soluble polymerizable compound of 3%～20 quality %.
14. image forming method according to claim 1, wherein in described ink composite, the content of described water-soluble polymerizable compound and described colored particles is than counting 1～30 by mass ratio.
15. image forming method according to claim 1, the viscosity of wherein said ink composite (25 ℃) is 1～10mPas.
16. image forming method according to claim 1 wherein when described ink composite comprises pigment as described colored particles, comprises the insoluble polymer dispersant as dispersant.
17. comprising, image forming method according to claim 16, wherein said insoluble polymer dispersant have the polyvinyl of carboxyl as the hydrophilic structure unit.
18. image forming method according to claim 1, wherein said ink composite comprises at least a resin particle.
19. image forming method according to claim 1, wherein the maximum adding quantity of described ink composite is 3～20ml/m when coating printing ink 2
20. image forming method according to claim 1, it also comprises:
With cumulative exposure is 10～5000mJ/cm 2Active energy beam irradiation be applied to ink composite on the recording medium.
CN201110078962.5A 2010-03-29 2011-03-28 Image forming method Expired - Fee Related CN102218907B (en)

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